JP2023095555A - dental adhesive kit - Google Patents

Abstract

To provide a dental adhesive kit that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to healthy dentin but also to dentin with a carious portion.SOLUTION: Provided is a dental adhesive kit, comprising: a dentin mineralizing agent (X) containing tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b); and a one agent-type self-adhesive dental composite resin (Y) containing a monomer (c) having an acidic group, a monomer (d) having no acidic group, and a water-soluble photoinitiator system (e) having a solubility in water of 10 g/L or more at 25°C, the content of the tetracalcium phosphate (a) being 1 to 80 pts.mass with respect to the total amount of 100 pts.mass of the dentin mineralizing agent (X), and the content of the alkali metal salt of phosphoric acid (b) being 1 to 100 pts.mass with respect to 100 pts.mass of the tetracalcium phosphate (a).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a dental bonding kit comprising a one-component self-adhesive dental composite resin and a dentin mineralizing agent. More specifically, the present invention relates to a dental adhesive kit that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to healthy dentin but also to dentine having caries.

BACKGROUND ART Conventionally, dental composite resins and dental prostheses are generally used for the treatment of dental caries and accompanying defects. The restorative treatment is usually performed according to the following procedure. If the defect is relatively small, the carious part is first scraped to form a cavity, then a dental bonding material is applied to the cavity, and then visible light is applied to the area where the dental bonding material has been applied to harden it. Let Next, the cured dental bonding material layer is filled with a dental composite resin, which is cured by irradiation with visible light. In addition, when the defect was relatively large, after similarly scraping the carious portion to form a cavity, a dental bonding material or a dental primer was applied to the bonding surfaces of the separately prepared dental prosthesis and the cavity. Above, a dental cement is used to bond the dental prosthesis and the tooth substance.

In the restoration method described above, a dental bonding material or a dental primer is used together with a dental composite resin or dental cement. have been developed and are beginning to be put to practical use as materials that can omit the use of dental bonding materials and dental primers and reduce the number of operating steps in restorative treatment.

Self-adhesive dental composite resins and dental cements have traditionally been made from dental materials such as cross-linking monomers to impart mechanical strength, fillers, and polymerization initiators to improve hardening properties. In addition to components that have been used in composite resins and dental cements, monomers with acidic groups that have been conventionally used in dental bonding materials are further included to impart adhesiveness to tooth substance ( For example, see Patent Documents 1 and 2). Further, Patent Document 3 proposes a dentinal tubule sealing material in which the curable composition has good adhesion to the surface of dentin, and a dental treatment material comprising a combination of the dentinal tubule sealing material and the curable composition. and self-adhesive composite resins are also described as curable compositions.

EP-A-2153811 Japanese Patent Application Publication No. 2015-507610 Japanese Unexamined Patent Application Publication No. 2013-82702

Adhesive Dentistry, Vol. 17, No. 3, pp. 186-191, 1999 Adhesive Dentistry, Vol.25, No.1, pp.12-18, 2007

By the way, in dental treatment, carious portions may be left intentionally or unintentionally. If you intentionally leave the carious part, if the carious part is small, use drugs such as antibacterial agents to keep the pulp as long as possible and to minimize the amount of tooth scraping. Minimally invasive treatments such as sterilization using

On the other hand, when a carious portion is present in the tooth, as described in Non-Patent Document 1, for example, in the carious dentin, the formation of the resin-impregnated layer is inhibited, so sufficient adhesiveness is not obtained. There was a difficulty that it was difficult to obtain Therefore, it is a challenge to obtain a dental composition that exhibits high adhesiveness (initial adhesive strength and adhesion durability) not only to healthy dentin without caries but also to dentine with caries. Become. However, the problem was a difficult problem that could not be sufficiently solved by the conventional techniques as described in Patent Documents 1 and 2. In addition, although the self-adhesive dental composite resin of Patent Document 3 is excellent in adhesiveness to healthy dentin, according to the investigations of the present inventors, the initial adhesive strength and adhesion durability to dentin in which carious portions are present have been found to be poor. found that there is room for improvement.

Accordingly, the present invention relates to a dental adhesive kit that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to healthy tooth structures but also to tooth structures with carious portions.

As a result of intensive studies, the present inventors have found that a dental adhesive kit comprising a dentin mineralizing agent of a specific composition and a one-component self-adhesive dental composite resin of a specific composition solves the above problems. After discovering that it can be done, the present invention was completed through repeated studies.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、及びＲ⁶は互いに独立して、炭素数１～４の直鎖状又は分岐鎖状のアルキル基又はハロゲン原子であり、Ｍは水素イオン、アルカリ金属イオン、アルカリ土類金属イオン、マグネシウムイオン、ピリジニウムイオン（ピリジン環が置換基を有していてもよい）、又はＨＮ⁺Ｚ¹Ｚ²Ｚ³（式中、Ｚ¹、Ｚ²、及びＺ³は互いに独立して、有機基又は水素原子）で示されるアンモニウムイオンであり、ｎは１又は２を表す。］
［７］２５℃での水への溶解度が１０ｇ／Ｌ未満である非水溶性還元剤（ｅ－３）と２５℃での水への溶解度が１０ｇ／Ｌ未満である非水溶性光増感剤（ｅ－４）とをさらに含む、［５］又は［６］に記載の歯科用接着キット。
［８］前記水溶性光重合開始剤システム（ｅ）が、２５℃での水への溶解度が１０ｇ／Ｌ以上である水溶性光増感剤（ｅ－２）と２５℃での水への溶解度が１０ｇ／Ｌ未満である非水溶性還元剤（ｅ－３）とを含む、［１］～［４］のいずれかに記載の歯科用接着キット。
［９］前記水溶性光重合開始剤システム（ｅ）が、２５℃での水への溶解度が１０ｇ／Ｌ未満である非水溶性光増感剤（ｅ－４）と２５℃での水への溶解度が１０ｇ／Ｌ以上である水溶性還元剤（ｅ－５）とを含む、［１］～［４］のいずれかに記載の歯科用接着キット。
［１０］前記水溶性光重合開始剤システム（ｅ）が、２５℃での水への溶解度が１０ｇ／Ｌ以上である水溶性光増感剤（ｅ－２）と２５℃での水への溶解度が１０ｇ／Ｌ以上である水溶性還元剤（ｅ－５）とを含む、［１］～［４］のいずれかに記載の歯科用接着キット。
［１１］前記酸性基を有しない単量体（ｄ）が、酸性基を有しない疎水性単量体（ｄ－１）を含む、［１］～［１０］のいずれかに記載の歯科用接着キット。
［１２］前記酸性基を有しない単量体（ｄ）が、酸性基を有しない親水性単量体（ｄ－２）をさらに含む、［１１］に記載の歯科用接着キット。
［１３］前記親水性単量体（ｄ－２）の含有量が、酸性基を有しない疎水性単量体（ｄ－１）と酸性基を有しない親水性単量体（ｄ－２）の総量１００質量部において５０質量部以下である、［１２］に記載の歯科用接着キット。
［１４］前記酸性基を有する単量体（ｃ）が、リン酸基を有する単量体である、［１］～［１３］のいずれかに記載の歯科用接着キット。
［１５］前記１材型の自己接着性歯科用コンポジットレジン（Ｙ）が、２５℃での水への溶解度が１０ｇ／Ｌ未満である非水溶性光重合開始剤システム（ｈ）をさらに含む、［１］～［１４］のいずれかに記載の歯科用接着キット。
［１６］前記１材型の自己接着性歯科用コンポジットレジン（Ｙ）において、水溶性光重合開始剤システム（ｅ）と非水溶性光重合開始剤システム（ｈ）の質量比［（ｅ）：（ｈ）］が、１０：１～１：１０である、［１５］に記載の歯科用接着キット。 That is, the present invention includes the following inventions.
[1] a dentin mineralizing agent (X) containing tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b);
A monomer (c) having an acidic group, a monomer (d) having no acidic group, and a water-soluble photopolymerization initiator system (e) having a solubility in water of 10 g/L or more at 25°C. A one-component self-adhesive dental composite resin (Y) containing
The content of the tetracalcium phosphate (a) is 1 to 80 parts by mass with respect to the total amount of 100 parts by mass of the dentin mineralizing agent (X), and the alkali metal salt of phosphoric acid (b) The content is 1 to 100 parts by mass with respect to 100 parts by mass of the tetracalcium phosphate (a),
Dental bonding kit.
[2] The dental adhesive kit according to [1], wherein the alkali metal salt of phosphoric acid (b) is disodium monohydrogen phosphate and/or monosodium dihydrogen phosphate.
[3] The dental adhesive kit according to [1] or [2], wherein the dentin mineralizing agent (X) further contains acid calcium phosphate (f).
[4] The acidic calcium phosphate (f) is anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogen phosphate [Ca(H ₂ PO ₄ ) ₂ ] particles, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] _particles , amorphous calcium phosphate [ _Ca3 ( _PO4 ) _{2.xH2O ] particles, calcium acid pyrophosphate [CaH2P2O7 ]} particles _, calcium monohydrogen phosphate dihydrate [ _CaHPO4 2H ₂ O] particles and calcium dihydrogen phosphate monohydrate [Ca(H ₂ PO ₄ ) 2.H ₂ O] particles, at least one selected from the group consisting of [3]. dental bonding kit.
[5] The water-soluble photopolymerization initiator system (e) contains a water-soluble cleavage-type photopolymerization initiator (e-1) having a solubility in water of 10 g/L or more at 25° C. [1] The dental adhesive kit according to any one of -[4].
[6] The water-soluble cleavage-type photopolymerization initiator (e-1) is at least one selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2). A dental adhesive kit according to [5].

[wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a halogen atom; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ¹ Z ² Z ³ (wherein Z ¹ , Z ² and Z ³ are each independently an ammonium ion represented by an organic group or a hydrogen atom), and n represents 1 or 2. ]
[7] A water-insoluble reducing agent (e-3) having a water solubility of less than 10 g/L at 25°C and a water-insoluble photosensitizer having a water solubility of less than 10 g/L at 25°C The dental adhesive kit according to [5] or [6], further comprising an agent (e-4).
[8] The water-soluble photoinitiator system (e) comprises a water-soluble photosensitizer (e-2) having a solubility in water at 25 ° C. of 10 g / L or more and water at 25 ° C. The dental adhesive kit according to any one of [1] to [4], further comprising a water-insoluble reducing agent (e-3) having a solubility of less than 10 g/L.
[9] The water-soluble photoinitiator system (e) is a water-insoluble photosensitizer (e-4) having a solubility in water at 25 ° C. of less than 10 g / L and water at 25 ° C. and a water-soluble reducing agent (e-5) having a solubility of 10 g/L or more.
[10] The water-soluble photoinitiator system (e) comprises a water-soluble photosensitizer (e-2) having a solubility in water at 25 ° C. of 10 g / L or more and a water-soluble photosensitizer at 25 ° C. The dental adhesive kit according to any one of [1] to [4], further comprising a water-soluble reducing agent (e-5) having a solubility of 10 g/L or more.
[11] The dental product according to any one of [1] to [10], wherein the monomer (d) having no acidic group comprises a hydrophobic monomer (d-1) having no acidic group. glue kit.
[12] The dental adhesive kit according to [11], wherein the monomer (d) having no acidic group further contains a hydrophilic monomer (d-2) having no acidic group.
[13] The content of the hydrophilic monomer (d-2) is a hydrophobic monomer (d-1) having no acidic group and a hydrophilic monomer (d-2) having no acidic group. The dental adhesive kit according to [12], which is 50 parts by mass or less in 100 parts by mass of the total amount of.
[14] The dental adhesive kit according to any one of [1] to [13], wherein the monomer (c) having an acidic group is a monomer having a phosphate group.
[15] The one-component self-adhesive dental composite resin (Y) further comprises a water-insoluble photopolymerization initiator system (h) having a solubility in water of less than 10 g/L at 25°C. The dental adhesive kit according to any one of [1] to [14].
[16] In the one-component self-adhesive dental composite resin (Y), the mass ratio of the water-soluble photoinitiator system (e) and the water-insoluble photoinitiator system (h) [(e): (h)] is 10:1 to 1:10, the dental adhesive kit according to [15].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a dental adhesive kit that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to healthy tooth structures but also to tooth structures with carious portions.

Preferred embodiments of the dental adhesive kit according to the present invention are described below. However, the present invention is by no means limited to the embodiments described below.

The dental adhesive kit of the present invention comprises a dentin mineralizing agent (X) and a one-component self-adhesive dental composite resin (Y). The dentin mineralizing agent (X) of the present invention is a composition containing tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b). The content of the tetracalcium phosphate (a) in the dentin mineralizing agent (X) is 1 to 80 parts per 100 parts by mass of the total amount of the dentin mineralizing agent (X). and the content of the alkali metal salt of phosphoric acid (b) is 1 to 100 parts by mass per 100 parts by mass of tetracalcium phosphate (a). part by mass. The one-material type self-adhesive dental composite resin (Y) of the present invention comprises a monomer (c) having an acidic group, a monomer (d) having no acidic group, and water at 25°C. It contains a water-soluble photopolymerization initiator system (e) having a solubility of 10 g/L or more (hereinafter simply referred to as "water-soluble photopolymerization initiator system (e)").

Although the mechanism by which the dental adhesive kit of the present invention exhibits the effects of the present invention is not clear, it is presumed as follows. In bonding dentin with caries, the resin-impregnated layer structure is rough and the dentin with caries is fragile compared to healthy dentin. It was thought that the adhesive strength was reduced. It is speculated that the dental adhesive kit of the present invention can form a strong resin-impregnated layer at the same time as strengthening dentin in which fragile carious portions exist. That is, a dentin mineralizing agent (X) containing certain amounts of tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b) is prepared in the presence of water, and applied to dentin having a carious portion. When applied, calcium ions obtained by dissolving tetracalcium phosphate (a) react with phosphate ions obtained by dissolving alkali metal salts of phosphoric acid (b) to form energetically stable hydroxyapatite. (HAp) precipitates. As a result, HAp is formed on the surface layer of fragile intertubular dentin, and HAp is precipitated deep into the dentinal tubules to seal the dentinal tubules, thereby strengthening the dentin in which fragile carious portions exist. It is estimated that Furthermore, by applying the one-component self-adhesive dental composite resin (Y) of the present invention to the strengthened dentin, a strong resin-impregnated layer is formed. The one-material type self-adhesive dental composite resin (Y) of the present invention contains the water-soluble photopolymerization initiator system (e), thereby improving the polymerization curability at the hydrophilic dentin interface. . Since tooth substance, especially dentin contains water, the interface is hydrophilic. It is necessary to form a resin-impregnated layer in which the monomer of the composite resin (Y) is permeated, and to increase the rate of polymerization to form a strong adhesive layer. The one-material type self-adhesive dental composite resin (Y) of the present invention is brought into contact with the dentin (wet body) surface by using the water-soluble photopolymerization initiator system (e), and is locally exposed to water. In the dissolved portion, the concentration of the water-soluble photopolymerization initiator system (e) becomes high, and the polymerization curability of the adhesive interface portion and the inside of the resin-impregnated layer can be selectively increased, forming a strong resin-impregnated layer. It is estimated that The two effects of strengthening dentin and forming a strong resin-impregnated layer work synergistically, so that the dental adhesive kit of the present invention has high adhesiveness (initial adhesive strength) even to dentin where caries exists. and adhesion durability).

Hereinafter, regarding the dental adhesive kit comprising the dentin mineralizing agent (X) and the one-material type self-adhesive dental composite resin (Y), each constituent material and each component used therein will be explained. In this specification, the upper limit and lower limit of the numerical range (content of each component, value calculated from each component, each physical property, etc.) can be combined as appropriate. In this specification, "(meth)acryl" is a generic term for methacryl and acryl, and the same applies to similar expressions.

Each component used in the dental adhesive kit of the present invention will be described below.

・Dentin mineralizing agent (X)
The dentin mineralizing agent (X) of the present invention contains tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b). A composition containing tetracalcium phosphate (a) is slowly converted to HAp when mixed in the presence of water.

The dentin mineralizing agent (X) contains 1 to 80 parts by mass of tetracalcium phosphate (a) with respect to 100 parts by mass of the total amount of the dentin mineralizing agent. If the content of tetracalcium phosphate (a) is less than 1 part by mass, the precipitation of HAp may be inhibited and the calcification effect may not be obtained. and more preferably 20 parts by mass or more. On the other hand, if the content of tetracalcium phosphate (a) exceeds 80 parts by mass, the precipitation of HAp may be inhibited and the calcification effect may not be obtained. It is more preferably 60 parts by mass or less, more preferably 60 parts by mass or less. Tetracalcium phosphate (a) is preferably in the form of particles in terms of dispersibility and dentinal tubule sealing properties.

The method for producing tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] (a) used in the present invention is not particularly limited. When the tetracalcium phosphate (a) is in the form of particles, commercially available tetracalcium phosphate particles may be used as they are, or may be used after being appropriately pulverized to adjust the particle size. As the pulverization method, the same method as the method for pulverizing acidic calcium phosphate (f), which will be described later, can be adopted.

When tetracalcium phosphate (a) is in the form of particles, the average particle size of the particles of tetracalcium phosphate (a) used in the present invention is preferably 0.5 to 40 μm. When the average particle size of the particles of tetracalcium phosphate (a) is 0.5 μm or more, the dissolution of tetracalcium phosphate (a) is adjusted to an appropriate amount, so that the pH in the aqueous solution does not become too high. , the precipitation of HAp can be facilitated, and the calcification effect can be easily obtained. The average particle size of the particles of tetracalcium phosphate (a) is more preferably 5 µm or more, and even more preferably 10 µm or more. On the other hand, when the average particle size of the particles of tetracalcium phosphate (a) is 40 μm or less, good paste properties such as sufficient viscosity can be obtained for the paste obtained by mixing with the liquid agent. In addition, there is little rough feeling during paste kneading, and the operability is excellent. The average particle size of the particles of tetracalcium phosphate (a) is more preferably 35 μm or less, further preferably 30 μm or less. The average particle size of the particles of tetracalcium phosphate (a) used in the present invention is calculated by measuring using a laser diffraction particle size distribution analyzer. The measurement method using a laser diffraction particle size distribution analyzer is the same as that for the filler (i) described below.

The dentin mineralizing agent (X) of the present invention contains 1 to 100 parts by mass of an alkali metal salt of phosphoric acid (b) per 100 parts by mass of tetracalcium phosphate (a). By containing a certain amount of an alkali metal salt of phosphoric acid (b) in addition to tetracalcium phosphate (a), a dentin mineralizing agent that has a high calcification effect and that precipitates HAp particularly deep into dentinal tubules. can provide. If the content of the alkali metal salt of phosphoric acid (b) is less than 1 part by mass, the precipitation of HAp may be inhibited and the calcification effect may not be obtained. More preferably, it is at least 1 part. On the other hand, if the content of the alkali metal salt of phosphoric acid (b) exceeds 100 parts by mass, the precipitation of HAp may be inhibited and the calcification effect may not be obtained. It is more preferably 95 parts by mass or less, and even more preferably 90 parts by mass or less.

The alkali metal salt of phosphoric acid (b) used in the present invention is not particularly limited, and disodium monohydrogen phosphate, dipotassium monohydrogen phosphate, monolithium dihydrogen phosphate, monosodium dihydrogen phosphate, phosphorus Monopotassium dihydrogenate, trisodium phosphate, tripotassium phosphate and the like can be mentioned, and one or more of these can be used. Among them, the alkali metal salt of phosphoric acid (b) is preferably disodium monohydrogen phosphate and/or monosodium dihydrogen phosphate from the viewpoint of easy availability of raw materials of high safety and purity. Moreover, from the viewpoint of safety, the alkali metal ion in the alkali metal salt of phosphoric acid (b) is preferably a sodium ion. The alkali metal salt of phosphoric acid (b) is preferably in the form of particles in terms of dispersibility and dentinal tubule sealing properties.

When the alkali metal salt of phosphoric acid (b) is in the form of particles, the average particle size of the particles of the alkali metal salt of phosphoric acid (b) used in the present invention is preferably 0.5 to 20 μm. When the average particle size of the particles of the alkali metal salt of phosphoric acid (b) is 0.5 μm or more, no significant aggregation occurs in the composition of the dentin mineralizing agent (X), and Since the alkali metal salt of phosphoric acid (b) can be uniformly dispersed, when the dentin mineralizing agent (X) of the present invention is converted to HAp, it suppresses the formation of holes in the HAp, and the formation of dentinal tubules. It is possible to suppress the decrease in blockage (dentine permeation inhibition rate). In terms of dispersibility and dentinal tubule sealing properties, the average particle size of the particles of the alkali metal salt of phosphoric acid (b) is more preferably 1 μm or more. On the other hand, when the average particle size of the particles of the alkali metal salt of phosphoric acid (b) is 20 μm or less, holes are formed in the HAp when the dentin mineralizing agent (X) of the present invention is converted to HAp. can be suppressed, and the deterioration of dentinal tubule sealing ability can be suppressed. In particular, hypersensitivity can be suppressed because the formation of such holes in dentinal tubules can be suppressed. In addition, when the paste is rubbed into the dentin surface to suppress dentin hypersensitivity, the undissolved alkali metal salt of phosphoric acid (b) does not remain in the paste and does not cause a rough feeling, resulting in excellent operability. The average particle size of the alkali metal salt of phosphoric acid (b) is more preferably 15 μm or less, more preferably 10 μm or less, because damage to dentin can also be suppressed. The average particle size of the alkali metal salt of phosphoric acid (b) used in the present invention is calculated by measuring using a laser diffraction particle size distribution analyzer. The measurement method using a laser diffraction particle size distribution analyzer is the same as that for the filler (i) described below.

The dentin mineralizing agent (X) of the present invention preferably contains an acidic calcium phosphate (f) in addition to the tetracalcium phosphate (a) and the alkali metal salt of phosphoric acid (b). This makes it possible to further enhance the calcification effect. For this reason, the present inventors have found that by containing an acidic calcium phosphate (f) with low solubility in addition to tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b), calcium ions and It is speculated that not only can phosphate ions be supplied for a longer period of time, but also the supply balance becomes more appropriate. From the standpoint of dispersibility and dentinal tubule sealing properties, the acid calcium phosphate (f) is preferably in the form of particles.

The acidic calcium phosphate (f) used in the present invention is not particularly limited, and includes anhydrous calcium monohydrogen phosphate [CaHPO ₄ ], anhydrous calcium dihydrogen phosphate [Ca(H ₂ PO ₄ ) ₂ ], tricalcium phosphate [ Ca ₃ (PO ₄ ) ₂ ], amorphous calcium phosphate [Ca ₃ (PO ₄ ) ₂ .xH ₂ O], calcium acid pyrophosphate [CaH ₂ P ₂ O ₇ ], calcium monohydrogen phosphate dihydrate [CaHPO ₄ ·2H2O] and calcium dihydrogen phosphate monohydrate [Ca(H ₂ PO ₄ ) 2·H ₂ O]. Among these, anhydrous calcium hydrogen phosphate [ _CaHPO4 ], anhydrous calcium dihydrogen _phosphate [Ca( _H2PO4 ) ₂ ] _, calcium monohydrogen phosphate dihydrate [ _CaHPO4.2H2O ], and calcium dihydrogen phosphate monohydrate [Ca(H ₂ PO ₄ ) 2.H ₂ O] is more preferably used, particularly anhydrous calcium hydrogen phosphate [CaHPO ₄ ], and anhydrous calcium dihydrogen phosphate [Ca(H ₂ PO ₄ ) ₂ ] is more preferably used.

When the acidic calcium phosphate (f) is in the form of particles, the average particle size of the particles of the acidic calcium phosphate (f) used in the present invention is preferably 0.1 to 7 μm. If the average particle size is less than 0.1 μm, there is a risk that the supply balance of calcium ions and phosphate ions will be disturbed due to excessive dissolution in the liquid agent, and the viscosity of the paste obtained by mixing with the liquid agent will be too high. and more preferably 0.3 μm or more. On the other hand, when the average particle size exceeds 7 μm, the acid calcium phosphate (f) becomes difficult to dissolve in the liquid preparation, and the tetracalcium phosphate (a) may dissolve excessively. As a result, the supply balance of calcium ions and phosphate ions is disturbed, and the pH of the aqueous solution becomes high, which may hinder the smooth precipitation of HAp and reduce the calcification effect. The average particle size of the particles of acidic calcium phosphate (f) is more preferably 3 μm or less. The average particle size of the particles of acidic calcium phosphate (f) is calculated in the same manner as the average particle size of the particles of tetracalcium phosphate (a).

The method for producing acidic calcium phosphate (f) having such an average particle size is not particularly limited, and if a commercially available product is available, it may be used, but it may be preferable to further pulverize the commercially available product. many. In that case, a pulverizing device such as a ball mill, a Raikai machine, a jet mill, or the like can be used. In addition, raw material powder of acidic calcium phosphate (f) is pulverized together with a liquid medium such as alcohol using a lykai machine, a ball mill, or the like to prepare a slurry, and the obtained slurry is dried to obtain acidic calcium phosphate (f). You can also get A ball mill is preferably used as the pulverizing device at this time, and alumina or zirconia is preferably used as the material of the pot and balls.

In a preferred embodiment, the dentin mineralizing agent (X) further contains acid calcium phosphate (f), the tetracalcium phosphate (a) is in the form of particles, and the particles of tetracalcium phosphate (a) The average particle size of the acidic calcium phosphate (f) is 0.5 to 40 μm, the average particle size of the particles of the acidic calcium phosphate (f) is 0.1 to 7 μm, and the average particle size of the tetracalcium phosphate (a) is the acidic calcium phosphate ( A dental adhesive kit comprising a dentin mineralizing agent (X) greater than the average particle size of the particles of f). By increasing the average particle size of the particles of tetracalcium phosphate (a) compared to the average particle size of the particles of acidic calcium phosphate (f), the solubility of the two is properly balanced, and the pH of the aqueous solution is brought to near neutrality. can be maintained. As a result, precipitation of HAp becomes smooth, and the calcification effect can be improved. Specifically, the average particle size of the particles of tetracalcium phosphate (a) is more preferably at least twice the average particle size of the particles of acidic calcium phosphate (f), and more preferably at least 4 times. Seven times or more is particularly preferred. On the other hand, the average particle size of the particles of tetracalcium phosphate (a) is more preferably 35 times or less, more preferably 30 times or less, and 25 times the average particle size of the particles of acidic calcium phosphate (f). The following are particularly preferred.

The mixing ratio ((a)/(f)) of tetracalcium phosphate (a) and acidic calcium phosphate (f) is not particularly limited, and the mixing ratio is such that the molar ratio is in the range of 40/60 to 60/40. preferably used. As a result, the dentin mineralizing agent (X) of the present invention having a high mineralization effect can be obtained. The blending ratio ((a)/(f)) is more preferably 45/55 to 55/45, most preferably substantially 50/50.

The dentin mineralizing agent (X) of the present invention preferably further contains a fluorine compound. This makes it possible to impart acid resistance to the dentin and promote calcification. The fluorine compound used in the present invention is not particularly limited, and includes sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, strontium fluoride, Barium fluoride, Copper fluoride, Zirconium fluoride, Aluminum fluoride, Tin fluoride, Sodium monofluorophosphate, Potassium monofluorophosphate, Hydrofluoric acid, Sodium titanium fluoride, Potassium titanium fluoride, Hexylamine hydro Fluoride, laurylamine hydrofluoride, glycine hydrofluoride, alanine hydrofluoride, fluorosilanes, diamine silver fluoride and the like. Among them, sodium fluoride, sodium monofluorophosphate, and tin fluoride are preferably used from the viewpoint of promoting calcification. The content of the fluorine compound is not particularly limited, and it is preferably 0.01 to 3 parts by mass of fluoride ions converted to the fluorine compound per 100 parts by mass of the total amount of the dentin mineralizing agent (X). If the content of converted fluoride ions in the fluorine compound is less than 0.01 parts by mass, the effect of promoting calcification may decrease, and it is more preferably 0.05 parts by mass or more. On the other hand, if the content of converted fluoride ions in the fluorine compound exceeds 3 parts by mass, safety may be impaired, and it is more preferably 1 part by mass or less.

The dentin mineralizing agent (X) of the present invention contains tetracalcium phosphate (a), an alkali metal salt of phosphoric acid (b), an acidic calcium phosphate (f) and a fluorine compound other than a It may contain ingredients. For example, a thickening agent can be blended as needed. Specific examples of thickeners include carboxymethylcellulose, sodium carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polystyrenesulfonic acid, polystyrenesulfonate, polyglutamic acid, polyglutamate, Polyaspartic acid, polyaspartate, poly-L-lysine, poly-L-lysine salt, starch other than cellulose, alginic acid, alginate, carrageenan, guar gum, xanthan gum, cellulose gum, hyaluronic acid, hyaluronate, pectin, One or more selected from polysaccharides such as pectin salts, chitin and chitosan, acidic polysaccharide esters such as propylene glycol alginate, and polymers such as proteins such as collagen, gelatin and derivatives thereof mentioned. The thickener is preferably at least one selected from sodium carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, alginic acid, alginate, chitosan, polyglutamic acid, and polyglutamic acid, in terms of water solubility and viscosity. The thickener may be blended into the powder, the liquid, or the paste being mixed. The content of the thickening agent is preferably 0.01 to 5 parts by mass per 100 parts by mass of the total amount of the dentin mineralization agent (X).

Inorganic fillers such as silica and metal oxides, if necessary; polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol and diglycerin; sugar alcohols such as xylitol, sorbitol and erythritol; polyethylene glycol and polypropylene glycol. artificial sweeteners such as aspartame, acesulfame potassium, licorice extract, saccharin, saccharin sodium, and the like. In one embodiment, the dentin mineralizing agent (X) of the present invention contains an inorganic filler from the viewpoint of operability and the ability to suppress aggregation of other particles containing tetracalcium phosphate (a). is preferred, and more preferably contains particles selected from silica or metal oxides having an average particle size of 0.002 to 2 μm, and silica particles having an average particle size of 0.002 to 2 μm. More preferred. The content of the inorganic filler in the dentin mineralizing agent (X) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the dentin mineralizing agent (X).

The dentin mineralizing agent (X) of the present invention can further contain pharmacologically acceptable agents and the like. The drug is not particularly limited as long as it is pharmacologically acceptable, and includes antibacterial agents such as cetylpyridinium chloride, disinfectants, anticancer agents, antibiotics, actocin, blood circulation improving agents such as PEG1, bFGF, PDGF, and BMP. Growth factors such as osteoblasts, odontoblasts, and differentiated cells such as undifferentiated bone marrow-derived stem cells, embryonic stem (ES) cells, fibroblasts, etc. are dedifferentiated and produced by gene transfer. (iPS: induced pluripotent stem) cells and cells that promote hard tissue formation such as differentiated cells.

In the dental adhesive kit of the present invention, the dentin mineralizing agent (X) was applied to the dentin surface, solid particles were filled in the dentin tubules, and then the dentin surface was adhered by rubbing with water. In a preferred embodiment, the solid component is removed and then a one-component self-adhesive dental composite resin (Y) is applied to the dentin surface from which the solid component has been removed and cured. That is, in the dental adhesive kit of the present invention, after the dentin mineralizing agent (X) is applied to the dentin surface and the inside of the dentin tubule is filled with solid particles, the dentin surface is rubbed with water. Since the adhering solid component can be removed, the adhesion is not hindered when the one-component self-adhesive dental composite resin (Y) is subsequently applied to the dentin surface and cured. In this way, before applying the one-component self-adhesive dental composite resin (Y) to the dentin surface, the surface layer of the fragile intercanal dentin is pretreated with the dentin mineralizing agent (X) of the present invention. As HAp is formed in the dentin surface, HAp is deposited deep in the dentinal tubules to seal the dentin tubules, thereby strengthening the dentin in which fragile carious portions are present. Adhesion of objects is also improved.

The dentin mineralizing agent (X) of the present invention is applied to the dentin surface and then applied to the dentin surface with a microbrush, cotton swab, rubber cup or the like in order to fill the solid particles into the dentin tubules. It is preferable to perform an operation of rubbing the applied dentin mineralizing agent (X) into the dentinal tubules. As for the rubbing operation, the dentin surface may be rubbed with a microbrush or the like for about 30 seconds, whereby the solid particles can be filled in the dentinal tubules.

In the present invention, the method for removing solid components adhering to the dentin surface by rubbing with water is not particularly limited, and an applicator such as a cotton ball, microbrush, sponge, cotton swab, or small brush soaked with water is used. Solid components adhering to the dentin surface can be preferably removed by scrubbing with.

・Single material self-adhesive dental composite resin (Y)
The one-material type self-adhesive dental composite resin (Y) of the present invention (hereinafter simply referred to as "self-adhesive dental composite resin (Y)") is made of tooth substance (enamel, dentin and cementum), comprising a monomer having an acidic group (c), a monomer having no acidic group (d), and a water-soluble photoinitiator system (e) contains Each component used in the self-adhesive dental composite resin (Y) of the present invention is described below.

<Monomer (c) having an acidic group>
The monomer (c) having an acidic group has an acid etching effect and a primer treatment effect, and is a component that imparts a demineralizing action and a penetrating action. Also, the monomer (c) having an acidic group is polymerizable and imparts a curing effect. By containing the monomer (c) having an acidic group, when combined with the dentin mineralizing agent (X), adhesiveness and adhesion not only to healthy dentin but also to dentin in which carious portions are present. Improves durability.

The monomer (c) having an acidic group has at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and an acryloyl group. , a methacryloyl group, a vinyl group and a styrene group. Specific examples of the monomer (c) having an acidic group are given below.

Examples of monomers having a phosphoric acid 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, 8-(meth) acryloyloxy octyl dihydrogen phosphate, 9-(meth) Acryloyloxy nonyl dihydrogen phosphate, 10-(meth) acryloyl oxydecyl dihydrogen phosphate, 11-(meth) acryloyl oxyundecyl dihydrogen phosphate, 12-(meth) acryloyl oxydecyl dihydrogen phosphate, 16-(meth) acryloyl oxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-( meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyloxyethylphenylhydrogenphosphate, 2-(meth)acryloyloxyethyl-2-bromo Ethylhydrogenphosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogenphosphate and their acid chlorides, alkali metal salts and ammonium salts.

Examples of the monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxy pyrophosphate]. hexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and ammonium salts thereof.

Monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyldihydrogenthiophosphate, 5-(meth)acryloyloxypentyldihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate, 8-(meth)acryloyloxyoctyldihydrogenthiophosphate Phosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyloxydecyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyicosyldihydrogenthiophosphate and acid chlorides, alkali metal salts and ammonium salts thereof.

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)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phospho Noacetates and their acid chlorides, alkali metal salts and ammonium salts are included.

Monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

The monomer having a carboxylic acid group includes a monomer having one carboxy group in the molecule and a monomer having a plurality of carboxy groups in the molecule.

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, 2-(meth)acryloyl Oxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2- Examples include (meth)acryloyloxyethylhydrogensuccinate, 2-(meth)acryloyloxyethylhydrogenphthalate, 2-(meth)acryloyloxyethylhydrogenmalate and acid halides thereof.

Examples of monomers having multiple carboxy 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)acryloyloxyundecane-1,1-dicarboxylic acid, 13-(meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)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 are exemplified.

Among these monomers having an acidic group (c), when a monomer having a phosphate group or a monomer having a pyrophosphate group is combined with the dentin mineralizing agent (X), healthy teeth A monomer having a phosphate group is particularly preferred because it exhibits excellent adhesiveness not only to tooth structure but also to tooth structure in which a carious portion exists. Among them, it exhibits high demineralization properties in the absence of organic solvents, and exhibits high adhesiveness even to tooth structures with caries. A monomer having a divalent phosphoric acid group having an alkyl group or an alkylene group is more preferable, and a monomer having an alkylene group having 8 to 12 carbon atoms as a main chain in the molecule such as 10-methacryloyloxydecyldihydrogen phosphate 2 More preferred are monomers having a monovalent phosphate group.

The monomer (c) having an acidic group may be used alone or in combination of two or more. 1 to 40 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (Y), from the viewpoint of good adhesion to tooth structures with caries and good water resistance of the cured product. parts, more preferably 2.5 to 35 parts by mass, even more preferably 5 to 30 parts by mass.

<Monomer (d) having no acidic group>
Examples of the monomer (d) having no acidic group include a hydrophobic monomer (d-1) having no acidic group and a hydrophilic monomer (d-2) having no acidic group.

<Hydrophobic monomer having no acidic group (d-1)>
In one embodiment, a one-component self-adhesive dental composite resin (Y ). The hydrophobic monomer (d-1) having no acidic group (hereinafter sometimes simply referred to as "hydrophobic monomer (d-1)") has no acidic group and has a polymerizable group is preferred, and the polymerizable group is more preferably a (meth)acryl group and/or a (meth)acrylamide group from the viewpoint of facilitating radical polymerization. The hydrophobic monomer (d-1) having no acidic group means one having no acidic group and having a solubility in water at 25° C. of less than 10 g/L, such as an aromatic compound Cross-linkable monomers such as bifunctional monomers of system, bifunctional monomers of aliphatic compounds, and monomers having trifunctional or higher functionality are exemplified. The hydrophobic monomer (d-1) improves the mechanical strength and handleability of the self-adhesive dental composite resin (Y).

Examples of aromatic compound-based bifunctional monomers 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 , 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropane) ethoxyphenyl)-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, 2 , 2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl ) propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (those with an average number of added moles of ethoxy groups of 2.6, commonly known as “D-2.6E”), 2,2-bis(4 -(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane is preferred.

Examples of aliphatic compound-based bifunctional monomers include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (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, 2,2,4-trimethylhexamethylenebis(2 -carbamoyloxyethyl)di(meth)acrylate, N-methacryloyloxyethylacrylamide, N-methacryloyloxypropylamide and the like. Among these, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), neopentyl glycol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2 , 2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA") is preferred. 1,10-decanediol dimethacrylate (commonly known as "DD"), 2, 2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate, N-methacryloyloxyethyl acrylamide (commonly known as "MAEA") is preferred.

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

Among the above hydrophobic monomers (d-1), from the viewpoint of handleability and mechanical strength of the cured product, aromatic compound-based bifunctional monomers and aliphatic compound-based bifunctional monomers Amers are preferably used. Bifunctional aromatic monomers include 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane and 2,2-bis(4-methacryloyloxypolyethoxy Phenyl)propane (having an average number of added moles of ethoxy groups of 2.6) is preferred. Examples of aliphatic compound-based bifunctional monomers include glycerol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 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 Methacrylates, N-methacryloyloxyethyl acrylamide are preferred.

Among the above hydrophobic monomers (d-1), from the viewpoint of initial adhesive strength and adhesion durability not only to healthy dentin but also to dentine with caries, and mechanical strength of the cured product, , Bis-GMA, D-2.6E, 3G, UDMA, DD and MAEA are more preferable, and Bis-GMA, 3G and UDMA are more preferable. Bis-GMA, D-2.6E, 3G, UDMA, DD, MAEA is more preferred, and D-2.6E, DD, and MAEA are even more preferred.

The hydrophobic monomer (d-1) may be blended alone or in combination of two or more. The content of the hydrophobic monomer (d-1) is the same as the content of the monomer in the self-adhesive dental composite resin (Y) from the viewpoint of the permeability of the composition into the dentin and the mechanical strength of the cured product. In the total amount of 100 parts by mass, the range is preferably 9 to 90 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 20 to 75 parts by mass. On the other hand, the content of the hydrophobic monomer (d-1) should be In the total amount of 100 parts by mass of the monomers in the self-adhesive dental composite resin (Y), it is preferably 40 to 99 parts by mass, more preferably 50 to 90 parts by mass, and 55 to 80 parts by mass. It is even more preferable to have

<Hydrophilic monomer having no acidic group (d-2)>
In one embodiment, a one-component self-adhesive dental composite resin ( Y). The hydrophilic monomer (d-2) having no acidic group (hereinafter sometimes simply referred to as "hydrophilic monomer (d-2)") does not have an acidic group and has a polymerizable group is preferred, and the polymerizable group is more preferably a (meth)acryl group and/or a (meth)acrylamide group from the viewpoint of facilitating radical polymerization. The hydrophilic monomer (d-2) having no acidic group means one having no acidic group and having a solubility in water at 25° C. of 10 g/L or more, and the solubility is 30 g/L. L or more are preferable, and those which are soluble in water at an arbitrary ratio at 25°C are more preferable. The hydrophilic monomer (d-2) promotes the penetration of the components of the self-adhesive dental composite resin (Y) into the tooth substance, and also penetrates into the tooth substance itself to collagen). The hydrophilic monomer (d-2) preferably has a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, and an amide group. For example, 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 ) hydrophilic monofunctional (meth)acrylate monomers such as ethyltrimethylammonium chloride and polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups); N-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 - Hydrophilic monomers such as (meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl(meth)acrylamide and monofunctional (meth)acrylamide-based monomers represented by the following general formula (di) Examples include functional (meth)acrylamide-based monomers.

（式（ｄ－ｉ）中、Ａ¹及びＡ²は互いに独立して、置換基を有していてもよい直鎖状又は分岐鎖状の炭素数１～３のアルキル基であり、Ａ³は水素原子又はメチル基である）

(In the formula (di), A ¹ and A ² are each independently an optionally substituted linear or branched alkyl group having 1 to 3 carbon atoms, and A ³ is a hydrogen atom or a methyl group)

As the substituents in A ¹ and A ² , the substituents of formula (1) can be similarly used. Examples of the alkyl group having 1 to 3 carbon atoms for A ¹ and A ² include methyl group, ethyl group, n-propyl group and isopropyl group.

Among the above hydrophilic monomers (d-2), 2-hydroxyethyl (meth)acrylate, 2,3- Dihydroxypropyl (meth) acrylate, a hydrophilic monofunctional (meth) acrylamide-based monomer is preferred, 2-hydroxyethyl (meth) acrylate, a monofunctional (meth) represented by the general formula (di) Acrylamide-based monomers are more preferred. The hydrophilic monomer (d-2) may be blended alone or in combination of two or more.

Further, among the monofunctional (meth)acrylamide-based monomers represented by the general formula (di), N,N-dimethylacrylamide and N,N-diethylacrylamide are more preferable from the viewpoint of storage stability. , N,N-diethylacrylamide is more preferred.

By including the hydrophilic monomer (d-2) in the self-adhesive dental composite resin (Y), the adhesive strength can be expected to be further improved, but if it is too much, the mechanical strength may decrease. Therefore, the content of the hydrophilic monomer (d-2) is preferably in the range of 9 to 90 parts by mass, and 15 to A range of 80 parts by mass is more preferable, and a range of 20 to 75 parts by mass is even more preferable. On the other hand, in order to exhibit a high initial adhesive strength and adhesion durability not only to healthy dentin but also to dentine with caries, the content of the hydrophilic monomer (d-2) is In the total amount of 100 parts by mass of the monomers in the self-adhesive dental composite resin (Y), it is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and 0 to 30 parts by mass. It is even more preferable to have The content of the hydrophilic monomer (d-2) may be 0 parts by mass. Further, in one embodiment, the content of the hydrophilic monomer (d-2) is such that the content of the hydrophilic monomer (d-1) having no acidic group and the hydrophilic monomer (d-1) having no acidic group It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, based on the total amount of 100 parts by mass of -2).

<Water-soluble photoinitiator system (e)>
The water-soluble photopolymerization initiator system (e) is effective when the self-adhesive dental composite resin (Y) contacts not only healthy tooth structure but also tooth structure (wet body) surface where caries exists. In the portion where the water-soluble photopolymerization initiator system (e) is dissolved, the concentration of the initiator becomes high, and polymerization occurs at the adhesion interface and inside the resin-impregnated layer. Brings about the effect of selectively enhancing curability.

The water-soluble photoinitiator system (e) 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 25 g/L or more. /L or more is more preferable. When the solubility is less than 10 g/L, when the self-adhesive dental composite resin (Y) of the present invention is applied to a wet body, the water-soluble photopolymerization initiator system (e) is added to the wet body at the adhesive interface. is not sufficiently dissolved in water, and as a result, the effect of accelerating polymerization becomes difficult to manifest.

Examples of the water-soluble photoinitiator system (e) include (i) a water-soluble cleavage-type photoinitiator (e-1), and (ii) a water solubility of 10 g/L or more at 25°C. a water-soluble photoinitiator system comprising a combination of a water-soluble photosensitizer (e-2) and a water-insoluble reducing agent (e-3) having a solubility in water of less than 10 g/L at 25°C; (iii) a water-insoluble photosensitizer (e-4) having a water solubility of less than 10 g/L at 25°C and a water-soluble reducing agent having a water solubility of 10 g/L or more at 25°C; (e-5) in combination with a water-soluble photoinitiator system, and (iv) a water-soluble photosensitizer (e-2) having a solubility in water at 25° C. of 10 g/L or more A water-soluble photopolymerization initiator system comprising a combination with a water-soluble reducing agent (e-5) having a solubility in water of 10 g/L or more at 25°C may be mentioned. These photopolymerization initiators and water-soluble photopolymerization initiator systems can be used singly or in combination of two or more. For example, when the water-soluble photopolymerization initiator system (e) contains a water-soluble cleavage-type photopolymerization initiator (e-1), as the polymerization initiator, only the water-soluble cleavage-type photopolymerization initiator (e-1) may be, in addition to the water-soluble cleavage-type photopolymerization initiator (e-1), further containing a water-insoluble reducing agent (e-3), and a water-insoluble photosensitizer (e-4) You can stay.
In the present invention, when the water-soluble photopolymerization initiator system (e) is the water-soluble photopolymerization initiator system (ii) to (iv) above, at least one of the agents constituting the system is water at 25 ° C. It is necessary that the solubility in is 10 g/L or more. The water-soluble photopolymerization initiator system (e) of the above (ii) to (iv) can exhibit a polymerization promoting effect as in the above (i) as long as the solubility of at least one agent satisfies the above conditions. When the water-soluble photopolymerization initiator system (e) corresponds to (ii) to (iv) above, the water-soluble photopolymerization initiator system (e) has a water solubility of 10 g/L or more at 25°C. "There is" means that at least one of the agents constituting the system has a solubility in water at 25°C of 10 g/L or more.

The water-soluble photopolymerization initiator system (e) dissolves in water not only on healthy teeth but also on the surface of teeth (wet bodies) where there are carious portions, and polymerizes the adhesive interface and the inside of the resin-impregnated layer. can be selectively increased, it may be dissolved in the self-adhesive dental composite resin (Y) or dispersed in the composition in powder form.

When the water-soluble photopolymerization initiator system (e) is dispersed in the composition in the form of powder, if the average particle size is too large, sedimentation tends to occur. More preferred are: On the other hand, if the average particle size is too small, the specific surface area of the powder will be too large and the amount that can be dispersed in the composition will decrease. That is, the average particle size of the water-soluble photopolymerization initiator system (e) is preferably in the range of 0.01-500 μm, more preferably in the range of 0.01-100 μm, and even more preferably in the range of 0.01-50 μm.

When the water-soluble photopolymerization initiator system (e) is dispersed in the composition in the form of powder, the shape of the photopolymerization initiator includes various shapes such as spherical, needle-like, plate-like, and crushed. is not particularly limited. The water-soluble photopolymerization initiator system (e) can be produced by conventionally known methods such as a pulverization method, a freeze-drying method, and a reprecipitation method. For example, it can be obtained by the following method.
Method 1: A method of preparing an aqueous solution of the water-soluble photopolymerization initiator system (e), freezing this aqueous solution at -50 ° C., and then vacuum-drying it in a frozen state;
Method 2: A method of preparing a saturated aqueous solution of the water-soluble photoinitiator system (e), pouring this aqueous solution into ethanol at 0 ° C., filtering the resulting crystals, washing with ethanol, and air drying;
Method 3: A method of preparing a saturated aqueous solution of the water-soluble photoinitiator system (e), rapidly cooling this aqueous solution to 0° C., filtering off the resulting crystals, and air-drying them; and Method 4. : A method of obtaining by mechanical grinding and sieving.

Among these methods for producing the water-soluble photopolymerization initiator system (e), the freeze-drying method (method 1) and the reprecipitation method (method 2) are preferable from the viewpoint of the average particle size of the resulting powder, and the freeze-drying method (Method 1) is more preferred.

The average particle size of the powder of each water-soluble photoinitiator system (e) is image analysis using image analysis software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron micrographs of 100 or more particles. It can be calculated as the volume average particle size after performing.

From the viewpoint of the curability of the self-adhesive dental composite resin (Y) obtained, the content of the water-soluble photopolymerization initiator system (e) is the same as that of the monomer in the self-adhesive dental composite resin (Y). 0.01 to 20 parts by mass is preferable with respect to 100 parts by mass of , more preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the content of the water-soluble photopolymerization initiator system (e) is 20 parts by mass or less, even when the polymerization performance of the water-soluble photopolymerization initiator system (e) is low, it is effective against dentin where caries exists. Furthermore, sufficient dissolution, dispersion, and diffusion in the self-adhesive dental composite resin (Y) are easily achieved.

Below, a water-soluble cleavage-type photopolymerization initiator (e-1), a water-soluble photosensitizer (e-2), a water-insoluble reducing agent (e-3), a water-insoluble photosensitizer (e- 4) and the water-soluble reducing agent (e-5) will be described in detail.

- A water-soluble cleavage-type photopolymerization initiator (e-1) having a solubility in water of 10 g/L or more at 25°C
Water-soluble cleavage-type photopolymerization initiators (e-1) include, for example, water-soluble acylphosphine oxides, water-soluble thioxanthones, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 - A (poly)ethylene glycol chain introduced into the hydroxyl group of methyl-1-propan-1-one, a (poly)ethylene glycol chain introduced into the hydroxyl group and/or phenyl group of 1-hydroxycyclohexylphenyl ketone, 1 -OCH ₂ COO ^- Na ⁺ introduced into the phenyl group of -hydroxycyclohexylphenyl ketone, (poly)ethylene glycol to the hydroxyl group and/or phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one α-Hydroxyalkylacetophenones such as those into which a chain is introduced and those in which —OCH ₂ COO ⁻ Na ⁺ is introduced into the phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one; 2-methyl- Amino groups of α-aminoalkylphenones such as 1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 and quaternary ammonium chloride. The water-soluble cleavage-type photopolymerization initiator (e-1) may be used alone or in combination of two or more.

Examples of the water-soluble acylphosphine oxides include compounds represented by the following general formula (1) and compounds represented by general formula (2).

[wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a halogen atom; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ¹ Z ² Z ³ (wherein Z ¹ , Z ² and Z ³ are each independently an ammonium ion represented by an organic group or a hydrogen atom), and n represents 1 or 2. ]

The alkyl groups for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not particularly limited as long as they are linear or branched and have 1 to 4 carbon atoms. ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group and the like. Pyridine ring substituents when M is a pyridinium ion include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, and a linear or branched acyl having 2 to 6 carbon atoms. groups, linear or branched alkyl groups having 1 to 6 carbon atoms, and linear or branched alkoxy groups having 1 to 6 carbon atoms. M is an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ¹ Z ² Z ³ (wherein the symbols are the above are preferred. Alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions. Alkaline earth metal ions include calcium ions, strontium ions, barium ions, and radium ions. Examples of the organic groups of Z ¹ , Z ² and Z ³ include the same substituents as those of the pyridine ring (excluding halogen atoms).

Among these, compounds in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are methyl groups exhibit excellent storage stability and color tone stability in self-adhesive dental composite resin (Y). It is preferable from the point of view. Ammonium ions include ammonium ions derived from various amines. Examples of amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylaminomethacrylate, N,N-dimethylaminobenzoic acid and its alkyl esters, N,N-diethylaminobenzoic acid and Its alkyl ester, N,N-bis(2-hydroxyethyl)-p-toluidine and the like.

Among these water-soluble acylphosphine oxides, phenyl(2,4,6-trimethylbenzoyl)phosphinate sodium salt, phenyl(2,4,6-trimethylbenzoyl)phosphinate lithium salt, bis(2,4,6 -trimethylbenzoyl)phosphinate sodium salt and bis(2,4,6-trimethylbenzoyl)phosphinate lithium salt are particularly preferred.

Water-soluble acylphosphine oxides having such a structure can be synthesized according to known methods, and some of them are commercially available. For example, it can be synthesized by the methods disclosed in JP-A-57-197289 and WO 2014/095724.

Examples of the water-soluble thioxanthones include 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy- 3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(9-oxo-9H-thio xanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N , N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium Chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride and the like can be used.

・Water-soluble photosensitizer (e-2)
Next, the water-soluble photosensitizer (e-2) will be described. In the self-adhesive dental composite resin (Y) of the present invention, the water-soluble photopolymerization initiator system (e) is a water-soluble photosensitizer ( In an embodiment including e-2), as a polymerization accelerator, a water-insoluble reducing agent (e-3) having a solubility in water of less than 10 g/L at 25°C and/or water at 25°C, which will be described later. The combined use of a water-soluble reducing agent (e-5) with a solubility of 10 g / L or more in the It is preferable from the point of exhibiting the property. The water-soluble photosensitizer (e-2) having a solubility in water of 10 g/L or more at 25° C. is preferably a compound represented by the following general formula (3). The water-soluble photosensitizer (e-2) having a solubility in water at 25° C. of 10 g/L or more may be used alone or in combination of two or more.

［式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は互いに独立して、水素原子、炭素数１～４の直鎖状もしくは分岐鎖状のアルキル基、炭素数１～４の直鎖状又は分岐鎖状のアルコキシ基、ハロゲン原子、－ＯＨ又は－ＣＯＯＹ¹であり、かつＲ⁸～Ｒ¹⁵の内の少なくとも１つは－ＣＯＯＹ¹であり、Ｙ¹は有機カチオン、又は無機カチオンを表す。］

[In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a linear or branched chain having 1 to 4 carbon atoms, an alkyl group, a linear or branched alkoxy group having 1 to 4 carbon atoms, a halogen atom, --OH or --COOY ¹ and at least one of R ⁸ to R ¹⁵ is --COOY ¹ , Y ¹ represents an organic cation or an inorganic cation. ]

The alkyl groups for R ⁸ to R ¹⁵ are not particularly limited as long as they are linear or branched having 1 to 4 carbon atoms, and include the same alkyl groups for R ¹ to R ⁶ . The alkyl group represented by R ⁸ to R ¹⁵ is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The alkoxy group represented by R ⁸ to R ¹⁵ is not particularly limited as long as it is linear or branched and has 1 to 4 carbon atoms. -butoxy group, sec-butoxy group, tert-butoxy group and the like. The alkoxy group is preferably a linear alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.

Y ¹ is an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ⁴ Z ⁵ Z ⁶ (wherein Z ⁴ , Z ⁵ and Z ⁶ each independently represent an organic group or a hydrogen atom) are preferred.

Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions. Examples of the alkaline earth metal ions include calcium ions, strontium ions, barium ions, and radium ions. When Y ¹ is a pyridinium ion, the pyridine ring substituents include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, and a linear or branched chain having 2 to 6 carbon atoms. Examples include an acyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms. Ammonium ions represented by HN ⁺ Z ⁴ Z ⁵ Z ⁶ include those derived from various amines. Examples of said amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylamino methacrylate, 4-(N,N-dimethylamino)benzoic acid and its alkyl esters, 4-( N,N-diethylamino)benzoic acid and its alkyl esters, N,N-bis(2-hydroxyethyl)-p-toluidine and the like. Examples of the organic groups of Z ⁴ , Z ⁵ and Z ⁶ include the same substituents as those of the pyridine ring (excluding halogen atoms). Among these, Y ¹ is preferably lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, ammonium ion represented by HN ⁺ Z ⁴ Z ⁵ Z ⁶ , lithium ion, sodium ion, potassium ion, Calcium ions and magnesium ions are more preferred, and lithium ions and sodium ions are even more preferred. For example, when Y ¹ is a divalent ion (eg, calcium ion), "--COOY ¹ " is expressed as "--COOCa _1/2 ". In other words, when Y ¹ is a divalent ion, the compound represented by general formula (3) forms a dimer.

The compound represented by formula (3) is preferably a compound in ^which at least one group among R ⁸ to R ¹⁵ is --COOY ^{1 ; 1} and the remaining groups of R ⁸ to R ¹⁵ are hydrogen atoms or methyl groups; at least one group ^of R ⁸ to R ¹⁵ is —COOY ¹ ; A compound in which the remaining groups of R ¹⁵ are hydrogen atoms or methyl groups and the number of methyl groups is 3 or less is more preferable; R ⁸ is a hydrogen atom or a methyl group and R ⁹ is a methyl group or -COOY ¹ When R ¹⁰ is a methyl group and (i) R ⁹ is a methyl group, any one of R ¹¹ to R ¹⁵ is —COOY ¹ , the other four are hydrogen atoms, and ( ii) When R ⁹ is —COOY ¹ , compounds in which R ¹¹ to R ¹⁵ are all hydrogen atoms are particularly preferred. Among these, R ⁸ is a hydrogen atom or a methyl group, R ⁹ and R ¹⁰ are methyl groups, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are all hydrogen atoms, and R ¹⁵ is a COOY Compound ¹ is most preferable from the viewpoint of adhesiveness not only to healthy teeth but also to teeth having caries.

A compound represented by general formula (3) having such a structure can be synthesized according to a known method.

Specific examples of the compound represented by formula (3) are not particularly limited, but include the following.

・ Water-insoluble reducing agent (e-3)
As another embodiment of the water-soluble photopolymerization initiator system (e) of the self-adhesive dental composite resin (Y) of the present invention, when the water-soluble photosensitizer (e-2) is included, it is used in combination. A water-insoluble reducing agent (e-3) may be used as a polymerization accelerator. Examples of water-insoluble reducing agents (e-3) include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, which have a solubility in water of less than 10 g/L at 25°C. copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, and the like. The water-insoluble reducing agent (e-3) may be used alone or in combination of two or more.

Amines used as the water-insoluble reducing agent (e-3) are classified into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-octylamine; secondary aliphatic amines such as dibutylamine; N-lauryldiethanolamine, N-ethyldiethanolamine dimethacrylate, triethanolamine dimethacrylate, tertiary aliphatic amines such as triethanolamine trimethacrylate and tributylamine; Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition. -(dimethylamino)ethyl methacrylate is more preferred.

Examples of aromatic amines include 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-di-isopropylaniline, N,N-bis(2-hydroxyethyl)- 3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N- Dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino) Methyl benzoate, 4-(N,N-dimethylamino) n-butoxyethyl benzoate, 4-(N,N-dimethylamino) 2-(methacryloyloxy) ethyl benzoate, 4-(N,N-dimethylamino) ) benzophenone and butyl 4-(N,N-dimethylamino)benzoate. Among these, ethyl 4-(N,N-dimethylamino)benzoate and 4-(N,N-dimethylamino)benzoate are used from the viewpoint of imparting excellent curability to the self-adhesive dental composite resin (Y). At least one selected from the group consisting of n-butoxyethyl acid and 4-(N,N-dimethylamino)benzophenone is preferably used.

Specific examples of sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogensulfites, and thiourea compounds include those described in International Publication No. 2008/087977.

- Water-insoluble photosensitizer (e-4)
As another embodiment of the water-soluble photopolymerization initiator system (e) of the self-adhesive dental composite resin (Y) of the present invention, when it contains a water-soluble reducing agent (e-5), it is used in combination. A water-insoluble photosensitizer (e-4) may be used as the photopolymerization initiator. Examples of water-insoluble photosensitizers (e-4) include thioxanthones, ketals, α-diketones, coumarins, anthraquinones, and benzoin, which have a water solubility of less than 10 g/L at 25°C. Examples include alkyl ether compounds and α-aminoketone compounds. The water-insoluble photosensitizer (e-4) may be used alone or in combination of two or more. The photoreaction between the photosensitizer and the reducing agent involves complex reactions such as hydrogen abstraction, and some points remain unclear. Both or either of the sensitizer and the reducing agent are water-soluble, so that the dental adhesive kit comprising the dentin mineralizing agent (X) and the self-adhesive dental composite resin (Y) can be used in the present invention. will bring about the effect of

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

Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of the α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. be done. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

Examples of the coumarin compound 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), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3- Benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3 -(4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin , 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho) [1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3′-carbonylbis(6-methoxycoumarin), 3,3′-carbonylbis(7-acetoxycoumarin), 3,3′- Carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzimidazolyl)-7 -(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3′-carbonylbis(7-dibutylaminocoumarin), 3 , 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]quinolidin-11-one, 10-(2-benzothiazolyl)- 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one, etc. -3109 and JP-A-10-245525.

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

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

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

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

Among these water-insoluble photosensitizers (e-4), it is preferable to use at least one selected from the group consisting of α-diketones and coumarin compounds.

・Water-soluble reducing agent (e-5)
As another embodiment of the water-soluble photopolymerization initiator system (e) of the self-adhesive dental composite resin (Y) of the present invention, a water-soluble photosensitizer (e-2) and/or a water-insoluble photosensitizer When the sensitizer (e-4) is contained, a water-soluble reducing agent (e-5) is used as a polymerization accelerator used in combination. Examples of the water-soluble reducing agent (e-5) include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, and copper, which have a solubility in water of 10 g/L or more at 25°C. compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, and the like.

［式中、Ｒ¹⁶及びＲ¹⁷は互いに独立して、炭素数１～４の直鎖状もしくは分岐鎖状のアルキル基であり、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹及びＲ²²は互いに独立して、水素原子、炭素数１～４の直鎖状又は分岐鎖状のアルキル基、炭素数１～４の直鎖状又は分岐鎖状のアルコキシ基、ハロゲン原子、－ＯＨ、－ＣＯＯＨ又は－ＣＯＯＹ²であり、かつＲ¹⁸～Ｒ²²の内の少なくとも１つは－ＣＯＯＨ、又は－ＣＯＯＹ²であり、Ｙ²は有機カチオン、又は無機カチオンを表す。］ Among the water-soluble reducing agents (e-5), it is particularly preferable to use the compound (e-5a) represented by the general formula (4) because it exhibits high adhesiveness to dentin.

[wherein R ¹⁶ and R ¹⁷ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a halogen atom, -OH, -COOH or --COOY ² , and at least one of R ¹⁸ to R ²² is --COOH or --COOY ² , and Y ² represents an organic cation or an inorganic cation. ]

The alkyl group for R ¹⁶ to R ²² is not particularly limited as long as it is linear or branched and has 1 to 4 carbon atoms, and is methyl, ethyl, n-propyl, isopropyl, n- butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group and the like. The alkyl group is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The alkoxy group represented by R ¹⁸ to R ²² is not particularly limited as long as it is linear or branched and has 1 to 4 carbon atoms. -butoxy group, sec-butoxy group, tert-butoxy group and the like. The alkoxy group is preferably a linear alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.

Y ² is an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ⁷ Z ⁸ Z ⁹ (wherein Z ⁷ , Z ⁸ and Z ⁹ independently of each other are preferably an ammonium ion represented by an organic group or a hydrogen atom).

Alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions. Alkaline earth metal ions include calcium ions, strontium ions, barium ions, and radium ions. When Y ² is a pyridinium ion, the substituents on the pyridine ring include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, and a linear or branched chain having 2 to 6 carbon atoms. Examples include an acyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms. Ammonium ions represented by HN ⁺ Z ⁷ Z ⁸ Z ⁹ include those derived from various amines. Examples of amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylamino methacrylate, 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. Examples of the organic groups for Z ⁷ , Z ⁸ and Z ⁹ include the same substituents as those for the pyridine ring (excluding halogen atoms). Among these, Y ² is preferably lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, ammonium ion represented by HN ⁺ Z ⁷ Z ⁸ Z ⁹ , lithium ion, sodium ion, potassium ion, Calcium ions and magnesium ions are more preferred, and lithium ions and sodium ions are even more preferred. For example, when Y ² is a divalent ion (eg, calcium ion), "--COOY ² " is expressed as "--COOCa _1/2 ". In other words, when Y ² is a divalent ion, the compound (e-5a) represented by general formula (4) forms a dimer.

As the compound (e-5a) represented by the general formula (4), R ¹⁶ and R ¹⁷ are methyl groups or ethyl groups, and at least one group among R ¹⁸ to R ²² is —COOH, or --COOY ² is preferred; R ¹⁶ and R ¹⁷ are methyl groups or ethyl groups, at least one group among R ¹⁸ to R ²² is --COOH or --COOY ² , and R ¹⁸ to Compounds in which at least one group among the remainder of R ²² is —OH or a linear alkoxy group having 1 to 3 carbon atoms are more preferred; R ¹⁶ and R ¹⁷ are methyl groups, and R ¹⁸ and R ¹⁹ is —COOH or —COOY ² , and at ^least one of R ²⁰ to R ²² is —OH or a ^methoxy group; R ¹⁹ , R 21 and ^R 22 when a methyl group and either one of R ¹⁸ and R ¹⁹ is -COOH or -COOY ² and (i) R ¹⁸ is ^-COOH or -COOY ² is a hydrogen atom, R ²⁰ is -OH or a methoxy group, and (ii) R ¹⁹ is -COOH or -COOY ² , R ¹⁸ , R ²⁰ and R ²² are hydrogen atoms, and R ²¹ Especially preferred are compounds in which is a --OH or methoxy group. Among these, when R ¹⁶ and R ¹⁷ are methyl groups, R ¹⁸ is —COOH or —COOY ² , R ¹⁹ , R ²¹ and R ²² are hydrogen atoms, and R ²⁰ is a methoxy group, It is most preferred from the viewpoint of adhesiveness to tooth substance.

Compound (e-5a) represented by general formula (4) having such a structure can be synthesized according to known methods, and some of them are commercially available.

Specific examples of the compound (e-5a) represented by formula (4) are not particularly limited, but include the following.

The self-adhesive dental composite resin (Y) of the present invention may contain a water-insoluble photoinitiator system (h).

<Water-insoluble photoinitiator system (h)>
From the viewpoint of curability, the self-adhesive dental composite resin (Y) of the present invention has a non-water-soluble polymer having a water solubility of less than 10 g/L at 25° C. in addition to the water-soluble photopolymerization initiator system (e). soluble photoinitiator system (h) (hereinafter simply referred to as "water-insoluble photoinitiator system (h)"). A known water-insoluble photopolymerization initiator can be used for the water-insoluble photopolymerization initiator system (h). The water-insoluble photoinitiator system (h) may be blended alone or in combination of two or more.

The water-insoluble photopolymerization initiator system (h) includes (bis)acylphosphine oxides other than the water-soluble cleavage-type photopolymerization initiator (e-1), α-diketones, and water-insoluble coumarin compounds. Photopolymerization initiator (h-1); a water-insoluble reducing agent (e-3) having a solubility in water of less than 10 g/L at 25°C and a water-insoluble reducing agent (e-3) having a solubility in water of less than 10 g/L at 25°C A water-insoluble photopolymerization initiator system (h-2), which is a combination with a certain water-insoluble photosensitizer (e-4), and the like. A preferred embodiment comprises a dentin mineralizing agent (X) and a self-adhesive dental composite resin (Y), wherein the self-adhesive dental composite resin (Y) is a monomer having an acidic group (c), a monomer having no acidic group (d), a water-soluble photopolymerization initiator system (e) containing a water-soluble cleavage-type photopolymerization initiator (e-1), and a water-insoluble photopolymerization initiator Adhesive dental material kits containing system (h) are included. In the self-adhesive dental composite resin (Y), when the water-soluble photoinitiator system (ii) to (iv) is used as the water-soluble photoinitiator system (e), water-insoluble A water-insoluble photopolymerization initiator system (h -2) may not be included.

Among the (bis)acylphosphine oxides, 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) phosphonates and the like. 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-trimethyl benzoyl)-2,4,4-trimethylpentylphosphine oxide and the like.

Among these water-insoluble photopolymerization initiators (h-1), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarin compounds. As a result, a self-adhesive dental composite resin ( Y) is obtained.

The content of the water-insoluble photopolymerization initiator system (h) is not particularly limited, but from the viewpoint of the curability of the resulting composition, the content of the water-insoluble photopolymerization initiator system (h) is self- With respect to 100 parts by mass of the total amount of monomers in the adhesive dental composite resin (Y), the range is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and 0.1 to 5 parts by mass. A range of parts by weight is more preferred. In addition, when the content of the water-insoluble photopolymerization initiator system (h) is 10% by mass or less, even when the polymerization performance of the water-insoluble photopolymerization initiator system (h) itself is low, carious portions are present. It is easy to obtain sufficient adhesiveness to the dentin that is to be treated, and furthermore, precipitation of the water-insoluble photopolymerization initiator system (h) itself from the self-adhesive dental composite resin (Y) can be suppressed.

The mass ratio [(e):(h)] of the water-soluble photoinitiator system (e) and the water-insoluble photoinitiator system (h) in the present invention is preferably 10:1 to 1:10. , more preferably 7:1 to 1:7, still more preferably 5:1 to 1:5, and particularly preferably 3:1 to 1:3. When the weight ratio of the water-soluble photopolymerization initiator system (e) does not exceed 10:1, the self-adhesive dental composite resin (Y) itself has excellent curability, and not only healthy teeth but also carious areas are present. It can express high initial adhesive strength and adhesive durability to the tooth structure. On the other hand, when the weight ratio of the water-insoluble photopolymerization initiator system (h) does not exceed 1:10, the curability of the self-adhesive dental composite resin (Y) itself is enhanced, and the polymerization of the adhesive interface is also accelerated. It progresses sufficiently, and can develop high initial adhesive strength and adhesion durability not only to healthy dentin, but also to dentin in which a carious portion exists.

<Chemical polymerization initiator>
The self-adhesive dental composite resin (Y) of the present invention may further contain a chemical polymerization initiator, preferably an organic peroxide. The organic peroxide used as the chemical polymerization initiator is not particularly limited, and known ones can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates, and the like. Specific examples of these organic peroxides include those described in International Publication No. 2008/087977.

In some embodiments, the self-adhesive dental composite resin (Y) of the present invention preferably further contains filler (i).

<Filler (i)>
Fillers (i) are generally classified into inorganic fillers, organic-inorganic composite fillers, and organic fillers. Filler (i) may be used individually by 1 type, and may use 2 or more types together.

Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramics. , aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, ytterbium oxide, silica-coated ytterbium fluoride and the like. These can also be used individually by 1 type or in mixture of 2 or more types. From the viewpoints of handling property and mechanical strength of the self-adhesive dental composite resin (Y), the average particle size of the inorganic filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. more preferred. In this specification, the average particle size of the filler means the average particle size of the primary particles of the filler (average primary particle size). In this specification, when the inorganic filler is surface-treated as described later, the average particle size of the inorganic filler means the average particle size before the surface treatment.

As for the shape of the inorganic filler, the shape of the inorganic filler is not particularly limited, and the particle size of the filler can be appropriately selected for use. Examples thereof include amorphous fillers and spherical fillers. From the viewpoint of improving the mechanical strength of the self-adhesive dental composite resin (Y), it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler means that the particles observed in the unit field of view of a photograph of the filler taken with a scanning electron microscope (hereinafter abbreviated as SEM) are rounded, and the particles in the direction orthogonal to the maximum diameter The filler has an average uniformity of 0.6 or more, which is obtained by dividing the diameter by the maximum diameter. The average particle size of the spherical filler is preferably 0.1 μm or more from the viewpoint that the filling rate of the spherical filler in the self-adhesive dental composite resin (Y) does not decrease and the mechanical strength can be maintained. is preferably 5 μm or less from the viewpoint that it is sufficient to maintain the mechanical strength of the resulting cured product.

In order to adjust the fluidity of the self-adhesive dental composite resin (Y), the inorganic filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent, if necessary. For example, by surface-treating the hydroxyl groups present on the surface of the inorganic filler with a silane coupling agent, it is possible to obtain an inorganic filler in which the hydroxyl groups are surface-treated. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoxyltrimethoxysilane, Examples include silane coupling agents such as 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane.

As the surface treatment method, known methods can be used without particular limitation. For example, a method of spraying the above surface treatment agent while vigorously stirring the inorganic filler, a method of adding the inorganic filler and the above surface treatment to an appropriate solvent. A method of removing the solvent after dispersing or dissolving the agent, or hydrolyzing the alkoxy group of the surface treatment agent in an aqueous solution with an acid catalyst to convert it to a silanol group, and attaching it to the surface of the inorganic filler in the aqueous solution. In any method, the reaction between the inorganic filler surface and the surface treatment agent is completed by heating in the range of usually 50 to 150 ° C., and the surface treatment is performed. It can be carried out. The surface treatment amount is not particularly limited, and for example, 1 to 10 parts by mass of the surface treatment agent can be used with respect to 100 parts by mass of the inorganic filler before treatment.

The organic-inorganic composite filler used in the present invention is obtained by previously adding a monomer compound to the inorganic filler described above, forming a paste, polymerizing the paste, and pulverizing the paste. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler are mixed, polymerized and pulverized) and the like 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 standpoint of handling properties and mechanical strength of the self-adhesive dental composite resin (Y), the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. It is more preferable to have

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, acrylonitrile-styrene-butadiene copolymer, etc., which may be used alone or It can be used 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 and used. From the standpoint of handling properties and mechanical strength of the self-adhesive dental composite resin (Y), the average particle size of the organic filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. is more preferred.

In addition, in this specification, the average particle size of the filler (i) can be determined by a laser diffraction scattering method or electron microscope observation of particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. 0.1 μm is a value measured by a laser diffraction scattering method.

Specifically, for example, laser diffraction scattering method is measured on a volume basis using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium using a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation). can do.

Electron microscope observation specifically, for example, a scanning electron microscope (manufactured by Hitachi, Ltd., model S-4000) to take a photograph of particles, particles (200 or more) particles observed in the unit field of view of the photograph The diameter can be determined by measurement using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountec Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

In the present invention, two or more fillers having different materials, particle size distributions, and morphologies may be mixed or used in combination. Particles other than i) may be contained as impurities. A commercially available product may be used as the filler in the present invention. Among them, from the viewpoint of the handleability and paste properties of the self-adhesive dental composite resin (X) of the present invention, the filler (i) is a filler (i-1) having an average particle size of 1 nm or more and less than 0.1 μm, Combination (I) with a filler (i-2) having an average particle diameter of 0.1 μm or more and 1 μm or less, a filler (i-1) having an average particle diameter of 1 nm or more and less than 0.1 μm, and a filler having an average particle diameter of more than 1 μm and 10 μm or less Combination (II) with (i-3), filler (i-1) with an average particle size of 1 nm or more and less than 0.1 μm, filler (i-2) with an average particle size of 0.1 μm or more and 1 μm or less, average particle size A combination (III) with a filler (i-3) of more than 1 μm and 10 μm or less, and a combination (IV) of a filler (i-2) having an average particle diameter of 0.1 μm or more and 1 μm or less are preferable. Among these combinations, (I), (II), and (III) are more preferred, and (I) and (II) are even more preferred, from the viewpoint of superior adhesion to the presence of caries. Combination (IV) of fillers (i-2) having an average particle size of 0.1 μm or more and 1 μm or less is an embodiment containing two types of fillers (i-2) having different average particle sizes of 0.1 μm or more and 1 μm or less. means In addition, if it is the said combination, the filler of a different kind may be contained in the filler (i) of each particle diameter. Moreover, particles other than the filler may be unintentionally contained as impurities within a range that does not impair the effects of the present invention.

The content of the filler (i) used in the self-adhesive dental composite resin (Y) is not particularly limited. It is preferably up to 2,000 parts by mass, more preferably 50 to 2,000 parts by mass, still more preferably 00 to 1,500 parts by mass, and particularly preferably 100 to 1,000 parts by mass. In one embodiment, the total amount of the self-adhesive dental composite resin (Y) is preferably 50 to 90 parts by mass, more preferably 55 to 85 parts by mass, and even more preferably 60 to 80 parts by mass.

<Fluoride ion-releasing substance>
The self-adhesive dental composite resin (Y) may further contain a fluoride ion-releasing substance. A self-adhesive dental composite resin (Y) capable of imparting acid resistance to tooth substance can be obtained by blending a fluoride ion-releasing substance. Examples of such fluoride ion-releasing substances include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion-releasing substances may be blended singly or in combination of two or more.

In addition, the self-adhesive dental composite resin (Y) may contain a pH adjuster such as N-methyldiethanolamine and triethanolamine, a polymerization inhibitor, a thickener, and a coloring agent, as long as they do not impair the effects of the present invention. (dyes, pigments), fluorescent agents, fragrances, and the like may be blended. These may be used individually by 1 type, and may use 2 or more types together. Antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxide decylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan may also be added. good.

As described above, the self-adhesive dental composite resin (Y) of the present invention may contain a small amount of water or an organic solvent (for example, The content of water and organic solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less, relative to the composition.

The present invention includes embodiments in which the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Also, not all combinations of features described in the embodiments are essential for the solution of the present invention. Various components used in the following examples and comparative examples, their abbreviations, structures, and test methods are as follows.

・Dentin mineralizing agent (X)
[Preparation of tetracalcium phosphate (a)]
The tetracalcium phosphate particles (average particle size: 5.0 μm, 9.2 μm) used in the present examples were products of Taihei Kagaku Sangyo Co., Ltd. and were used as they were.

[Preparation of alkali metal salt of phosphoric acid (b)]
Sodium monohydrogen phosphate (average particle diameter: 4.6 μm) used in this example was prepared by dissolving commercially available sodium monohydrogen phosphate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using Nano Jet Mizer (NJ-100 type, manufactured by Co., Ltd.). Aisin Nano Technologies), the pulverization pressure conditions were raw material supply pressure: 0.7 MPa/pulverization pressure: 0.7 MPa, and the processing amount condition was 8 kg/hr, and one treatment was performed.

[Preparation of acidic calcium phosphate (f)]
Anhydrous calcium monohydrogen phosphate (DCPA) particles (average particle diameter 1.1 μm) used in this example are commercially available anhydrous calcium monohydrogen phosphate particles (manufactured by Taihei Kagaku Sangyo Co., Ltd., average particle diameter 15.0 μm). 50 g, 95% ethanol ("Ethanol (95)" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 120 g, and 240 g of zirconia balls with a diameter of 10 mm are added to a 400 ml alumina grinding pot ("Type A-3 HD" manufactured by Nikkato Co., Ltd. Pot mill") and wet pulverization at a rotation speed of 120 rpm for 24 hours. The slurry obtained by distilling off ethanol with a rotary evaporator is dried at 60 ° C. for 6 hours, and further vacuumed at 60 ° C. for 24 hours. Obtained by drying.

・Self-adhesive dental composite resin (Y)
[Monomer (c) having an acidic group]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Hydrophobic monomer having no acidic group (d-1)]
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate 3G: tri Ethylene glycol dimethacrylate

[Hydrophilic monomer having no acidic group (d-2)]
HEMA: 2-hydroxyethyl methacrylate DEAA: N,N-diethylacrylamide

２５℃での水への溶解度：４５ｇ／Ｌ [Water-soluble photoinitiator system (e)]
- Water-soluble cleavage-type photopolymerization initiator (e-1)
Li-TPO: Lithium phenyl (2,4,6-trimethylbenzoyl)phosphinate (compound represented by the following formula (5))

Solubility in water at 25°C: 45 g/L

２５℃での水への溶解度：２８ｇ／Ｌ Na-TPO: sodium phenyl(2,4,6-trimethylbenzoyl)phosphinate (compound represented by the following formula (6))

Solubility in water at 25°C: 28 g/L

２５℃での水への溶解度：５２ｇ／Ｌ BAPO-OLi: Lithium bis(2,4,6-trimethylbenzoyl)phosphinate (compound represented by the following formula (7))

Solubility in water at 25°C: 52 g/L

２５℃での水への溶解度：６０ｇ／Ｌ BAPO-ONa: sodium bis(2,4,6-trimethylbenzoyl)phosphinate (compound represented by the following formula (8))

Solubility in water at 25°C: 60 g/L

２５℃での水への溶解度：＞１０ｇ／Ｌ ・Water-soluble sensitizer (e-2)
CQ-COONa (compound represented by the following formula (9))

Solubility in water at 25°C: >10 g/L

・ Water-insoluble reducing agent (e-3)
DABE: 4-(N,N-dimethylamino)ethyl benzoate Solubility in water at 25°C: <1 g/L

- Water-insoluble photosensitizer (e-4)
CQ: dl-camphorquinone Solubility in water at 25°C: 1.7 g/L

２５℃での水への溶解度：＞１０ｇ／Ｌ ・Water-soluble reducing agent (e-5)
AMN-COOLi (compound represented by the following formula (10))

Solubility in water at 25°C: >10 g/L

２５℃での水への溶解度：＜１０ｇ／Ｌ [Water-insoluble photoinitiator (h-1)]
TMDPO-A1 (compound represented by the following formula (11))

Solubility in water at 25°C: <10 g/L

２５℃での水への溶解度：＜１０ｇ／Ｌ BAPO-A1 (compound represented by the following formula (12))

Solubility in water at 25°C: <10 g/L

TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide Solubility in water at 25°C: <1 g/L
BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide Solubility in water at 25°C: <1 g/L

[Filler (i)]
Inorganic filler 1: Fine particle silica "Aerosil (registered trademark) 380" manufactured by Nippon Aerosil Co., Ltd., average particle size: 7 nm
Inorganic filler 2: Silane-treated silica powder Silica stone powder (manufactured by Nitschitsu Co., Ltd., trade name: Hi-Silica) was pulverized with a ball mill to obtain pulverized silica powder. The average particle size of the pulverized silica powder obtained was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.2 µm. 100 parts by mass of this pulverized silica powder was surface-treated with 4 parts by mass of γ-methacryloyloxypropyltrimethoxysilane in a conventional manner to obtain silane-treated silica powder.
Inorganic Filler 3: Silane-treated Barium Glass Powder Barium glass (trade name “E-3000” manufactured by Estech) was pulverized with a ball mill to obtain barium glass powder. The average particle size of the obtained barium glass powder was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.4 µm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane in a conventional manner to obtain silane-treated barium glass powder.

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

[Examples 1 to 17 and Comparative Examples 1 to 6]
[Preparation of powder of dentin mineralizing agent]
26.2 g of particles of tetracalcium phosphate (a), 5 g of particles of disodium monohydrogen phosphate (b), 9.8 particles of anhydrous calcium monohydrogen phosphate (f) and disclosed in JP-A-2-258602 Add 0.21 g of sodium fluoride particles (average particle size 0.7 μm) micronized by the method of No. 1 to a high-speed rotating mill (“SM-1” manufactured by AS ONE Co., Ltd.) and mix for 3 minutes at a rotation speed of 1000 rpm. A powder of dentin mineralizing agent was obtained.

[Preparation of dentin mineralizing agent (X)]
A paste-like dentin mineralizing agent was prepared by mixing the dentin mineralizing agent powder obtained above and purified water at a mass ratio of dentin mineralizing agent powder/purified water=1.2.

[Preparation of one-component self-adhesive dental composite resin (Y)]
The raw materials shown in Tables 1 to 3 were mixed and kneaded at room temperature (23° C.) in the dark to prepare a paste-like one-component self-adhesive dental composite resin, and the properties were measured according to the method of Test Example 1 below. Examined.

[Preparation of artificial demineralized dentin]
Artificial demineralized dentin was prepared in the following manner assuming tooth material with caries. That is, first, the lip surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample in which the flat surface of the dentin was exposed. The obtained sample was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. Next, referring to the description of the preparation of artificial demineralized dentin in Non-Patent Document 2, after coating the tooth surface excluding the central portion (4 mm × 4 mm) of the exposed dentin surface with nail varnish, a 1 N KOH aqueous solution was applied. 2.2 mmol/L CaCl ₂ , 2.2 mmol/L Na ₂ HPO ₄ , and 50 mmol/L CH ₃ COOH. Demineralized dentin was formed on the exposed dentin surface.

[Test Example 1: Tensile bond strength to artificial demineralized dentin]
The artificial demineralized dentin prepared as described above was washed under running water and dried by air blowing water on the surface. A microbrush was used to rub a dentin mineralizing agent over a 4 mm×4 mm area of the dentin surface of the smooth surface after drying (where demineralized dentin was formed) for 30 seconds. Next, the dentin surface was cleaned for 10 seconds with a cotton ball moistened with water to remove the paste microparticles slightly remaining on the surface, thereby forming a dentin mineralizing agent-treated surface.

An adhesive tape having a thickness of about 150 μm and having a round hole with a diameter of 3 mm was adhered to the dentin mineralizing agent-treated surface of the adherend sample to define the adhesion area. The self-adhesive dental composite resin prepared in each of the above Examples or Comparative Examples was filled in the round hole and covered with a release film (polyester). Next, a slide glass was placed on the release film and pressed to smooth the coating surface of the self-adhesive dental composite resin. Subsequently, through the release film, the self-adhesive dental composite resin is irradiated with light for 10 seconds using a dental LED light irradiator (manufactured by Ultradent, trade name “VALO”). , cured the self-adhesive dental composite resin.
A commercially available dental resin cement (manufactured by Kuraray Noritake Dental Co., Ltd., trade name "Panavia (registered trademark) 21") was applied to the surface of the hardened self-adhesive dental composite resin to form a stainless steel column. One end face (circular cross-section) of a rod (diameter 7 mm, length 2.5 cm) was glued. After adhesion, the sample was allowed to stand at room temperature for 30 minutes, and then immersed in distilled water to obtain an adhesion test sample. Twenty test samples for the adhesion test were prepared for each example or comparative example, and while being immersed in distilled water, they were allowed to stand in a constant temperature vessel maintained at 37° C. for 24 hours.
Ten of the 20 samples were measured for tensile bond strength immediately after standing for 24 hours as described above to assess initial bond strength. The tensile bond strength was measured using a universal testing machine (manufactured by Shimadzu Corporation) with a crosshead speed of 2 mm/min. The average value of the obtained tensile bond strength values was taken as the initial bond strength.
In addition, in order to evaluate the adhesion durability, the remaining 10 samples were further subjected to 4000 cycles of heat cycles, in which one cycle was alternately immersed in cold water at 4 ° C. and hot water at 60 ° C. for 1 minute. , the tensile bond strength was measured in the same manner as above. The average value of the obtained tensile bond strength values was defined as bond durability.

As is clear from the above results, the dental adhesive kit (Examples 1 to 17) according to the present invention has an initial adhesive strength of 11 MPa to artificial demineralized dentin, which is assumed to be tooth with caries. Demonstrating a tensile adhesive strength of 10 MPa or more as an adhesive durability, and exhibiting high adhesiveness (initial adhesive strength and adhesive durability) even to dentin where caries exists. I found out.

On the other hand, in the dental adhesive kits of Comparative Examples 1 to 5, which do not satisfy the configuration of the present invention, the initial adhesive strength to artificial demineralized dentin is 6.9 MPa even when high, and the adhesive durability is 3.3 MPa. It was below. In addition, in Comparative Example 6, in which only the self-adhesive dental composite resin was used without using the dentin mineralizing agent (X) of the present invention, the adhesion durability was 3.7 MPa.

A dental adhesive kit comprising a dentin mineralizing agent and a self-adhesive dental composite resin according to the present invention can be suitably used for dental restorative treatment.

Claims (16)

a dentin mineralizing agent (X) containing tetracalcium phosphate (a) and an alkali metal salt of phosphoric acid (b);
A monomer (c) having an acidic group, a monomer (d) having no acidic group, and a water-soluble photopolymerization initiator system (e) having a solubility in water of 10 g/L or more at 25°C. A one-component self-adhesive dental composite resin (Y) containing
The content of the tetracalcium phosphate (a) is 1 to 80 parts by mass with respect to the total amount of 100 parts by mass of the dentin mineralizing agent (X), and the alkali metal salt of phosphoric acid (b) The content is 1 to 100 parts by mass with respect to 100 parts by mass of the tetracalcium phosphate (a),
Dental bonding kit. 2. A dental adhesive kit according to claim 1, wherein the alkali metal salt of phosphoric acid (b) is disodium monohydrogen phosphate and/or monosodium dihydrogen phosphate. 3. A dental adhesive kit according to claim 1 or 2, wherein said dentin mineralizing agent (X) further contains acid calcium phosphate (f). The acidic calcium phosphate (f) is anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogen phosphate [Ca(H ₂ PO ₄ ) ₂ ] particles, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] particles, amorphous calcium phosphate [Ca ₃ (PO ₄ ) ₂ .xH ₂ O] particles, calcium acid pyrophosphate [CaH ₂ P ₂ O ₇ ] particles, calcium monohydrogen phosphate dihydrate [CaHPO ₄ .2H ₂ O] particles and calcium dihydrogen phosphate monohydrate [Ca(H ₂ PO ₄ ) 2.H ₂ O] particles. glue kit. Claims 1 to 4, wherein the water-soluble photopolymerization initiator system (e) comprises a water-soluble cleavage-type photopolymerization initiator (e-1) having a solubility in water of 10 g/L or more at 25°C. A dental adhesive kit according to any one of the preceding claims. The water-soluble cleavage-type photopolymerization initiator (e-1) is at least one selected from the group consisting of compounds represented by the general formula (1) and compounds represented by the general formula (2). Item 6. A dental adhesive kit according to item 5.

[wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a halogen atom; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN ⁺ Z ¹ Z ² Z ³ (wherein Z ¹ , Z ² and Z ³ are each independently an ammonium ion represented by an organic group or a hydrogen atom), and n represents 1 or 2. ] A water-insoluble reducing agent (e-3) having a water solubility of less than 10 g/L at 25°C and a water-insoluble photosensitizer (e-3) having a water solubility of less than 10 g/L at 25°C -4). The water-soluble photoinitiator system (e) is a water-soluble photosensitizer (e-2) having a solubility in water of 10 g / L or more at 25 ° C. and a solubility in water of 10 g at 25 ° C. The dental adhesive kit according to any one of claims 1 to 4, comprising a water-insoluble reducing agent (e-3) that is less than /L. The water-soluble photoinitiator system (e) is a water-insoluble photosensitizer (e-4) having a solubility in water of less than 10 g / L at 25 ° C. and a solubility in water at 25 ° C. The dental adhesive kit according to any one of claims 1 to 4, further comprising a water-soluble reducing agent (e-5) of 10 g/L or more. The water-soluble photoinitiator system (e) is a water-soluble photosensitizer (e-2) having a solubility in water of 10 g / L or more at 25 ° C. and a solubility in water of 10 g at 25 ° C. /L or more of the water-soluble reducing agent (e-5). The dental adhesive kit according to any one of claims 1 to 10, wherein the monomer (d) having no acidic group comprises a hydrophobic monomer (d-1) having no acidic group. 12. The dental adhesive kit according to claim 11, wherein the monomer (d) having no acidic group further comprises a hydrophilic monomer (d-2) having no acidic group. The content of the hydrophilic monomer (d-2) is the total amount of the hydrophobic monomer (d-1) having no acidic group and the hydrophilic monomer (d-2) having no acidic group: 100 13. The dental adhesive kit according to claim 12, which is 50 parts by mass or less. The dental adhesive kit according to any one of claims 1 to 13, wherein the monomer (c) having an acidic group is a monomer having a phosphate group. Claim 1, wherein the one-component self-adhesive dental composite resin (Y) further comprises a water-insoluble photoinitiator system (h) having a solubility in water of less than 10 g/L at 25°C. 15. A dental bonding kit according to any one of 14. In the one-component self-adhesive dental composite resin (Y), the mass ratio of the water-soluble photoinitiator system (e) and the water-insoluble photoinitiator system (h) [(e):(h) ] is between 10:1 and 1:10.