JP2022172925A - dental filling kit - Google Patents

Abstract

To provide a dental filling kit that demonstrates excellent cavity sealability and dentin bondability by a simple method of filling a cavity with a self-adhesive dental composite resin and then filling its top with glass ionomer cement.SOLUTION: A dental filling kit contains: a self-adhesive dental composite resin (X) that contains an acidic group-containing monomer (a), an acidic group-free monomer (b), and a photopolymerization initiator (c); and a glass ionomer cement (Y) that contains fluoroaluminosilicate glass powder (f), a polycarboxylic acid polymer (g), and water (h). The content of the acidic group-containing monomer (a) is 1-30 pts.mass relative to 100 pts.mass of the total monomer content of the (a) self-adhesive dental composite resin (X).SELECTED DRAWING: Figure 1

Description

The present invention relates to dental filling kits. More specifically, in the dental filling kit of the present invention, a cavity is filled with a self-adhesive dental composite resin, and then the upper portion is filled with a glass ionomer cement. It also relates to a dental filling kit that achieves both the strength of bonding with tooth substance.

To restore tooth structure (enamel, dentin, and cementum) damaged by caries, etc., we usually use filling and restorative materials such as filling composite resins and filling compomers, as well as tooth materials such as metal alloys, porcelain, and resin materials. A crown restorative material is used. However, in general, filling restorative materials and crown restorative materials (in this specification, both are collectively referred to as "dental restorative materials") themselves do not have adhesiveness to tooth substance. For this reason, conventionally, various bonding systems using adhesives have been used for bonding tooth substance and dental restorative materials. As a conventionally widely used adhesive system, after etching the surface of the tooth using an acid etching agent such as an aqueous phosphoric acid solution, a bonding material is applied as an adhesive to attach the tooth to the dental surface. There are so-called acid etching type (total etching type) bonding systems for bonding with repair materials.

On the other hand, there is a so-called self-etching adhesive system as an adhesive system that does not use an acid etchant. This adhesive system has conventionally been applied to the tooth surface with a self-etching primer containing an acidic monomer, a hydrophilic monomer and water, and then without washing with water. A two-step adhesive system that applies the material used to be the mainstream, but recently, a one-step adhesive that uses a one-component dental adhesive (one-component bonding material) that has both the functions of a self-etching primer and a bonding material. adhesive systems are commonly used. One-liquid type bonding materials generally contain acidic monomers, hydrophilic monomers, cross-linking monomers, etc. as monomer components, and water and hydrophilic volatile organic solvents are generally used.

In addition, recently, a self-adhesive dental composite resin has been developed, which is a dental composite resin with adhesive properties, and compositions that omit the use of bonding materials and reduce the number of operating steps in restorative treatment have begun to be put into practical use. (Patent Documents 1 to 3). Furthermore, dental restorative material kits such as Patent Documents 4 and 5 have also been proposed. In general, bonding materials differ from dental composite resins (self-adhesive dental composite resins, etc.) in that they contain solvents (water, organic solvents, etc.) and contain fillers.

Japanese translation of PCT publication No. 2004-529946 JP 2017-105716 A JP 2018-065831 A Japanese Patent Application Laid-Open No. 2006-131621 WO2020/195026

However, the self-adhesive dental materials and self-adhesive dental composite resins described in Patent Documents 1 to 3, according to examinations by the present inventors, were found to have no cavity sealing properties according to actual clinical tests. It turned out that there was a problem.

In addition, for example, after applying a bonding material as in Patent Document 4, a dental composite resin containing an acidic group-containing monomer is used and light irradiation is performed all at once. applying a glass ionomer cement to the area of the tooth; curing the applied glass ionomer cement; and containing a (meth)acrylate having an acid group in a predetermined area of the tooth where the glass ionomer cement is cured. A dental restorative set to which a composite resin is applied has been proposed.

However, in the method of Patent Document 4, it was found that, for example, a shade with low transparency has a small hardening depth, so that the hardening property of the bonding material is low and the cavity sealing property is low. Furthermore, in the method of Patent Document 5, since the adhesive strength of the glass ionomer cement to the dentin is lower than that of the dental composite resin containing (meth)acrylate having an acidic group, it cannot be said that the cavity sealing property is sufficient. In addition, the operation was complicated because it was necessary to use a conditioner together. In addition, in Patent Document 5, in order to solve the problem that the adhesiveness of the cured composite resin to the cured glass ionomer cement is reduced, considering the curing depth due to the transparency of the dental composite resin, It was thought that a glass ionomer cement should be applied to the fossa-bottom side of the dentin and a dental composite resin should be applied thereover (see US Pat.

According to the present invention, by filling the cavity with a self-adhesive dental composite resin and then filling the upper portion with a glass ionomer cement, it is possible to achieve excellent cavity sealing performance and adhesion strength to the dentin by a simple method. It is an object of the present invention to provide a dental filling kit that exhibits

As a result of intensive studies, the present inventor found that a dental filling kit comprising a self-adhesive dental composite resin of a specific composition and a glass ionomer cement of a specific composition can solve the above problems, and further investigations have been made. The present invention has been completed through repeated efforts.

That is, the present invention includes the following inventions.
[1] a self-adhesive dental composite resin (X) comprising a monomer (a) having an acidic group, a monomer (b) having no acidic group, and a photopolymerization initiator (c);
A fluoroaluminosilicate glass powder (f), a polycarboxylic acid polymer (g), and a glass ionomer cement (Y) containing water (h),
A dental filling kit, wherein the content of the monomer (a) having an acidic group is 1 to 30 parts by mass per 100 parts by mass of the total amount of monomers of the self-adhesive dental composite resin (X).
[2] The self-adhesive dental composite resin (X) further contains a filler (d), and the content of the filler (d) is 100 parts by mass in total of the self-adhesive dental composite resin (X), The dental filling kit according to [1], which is 50 to 90 parts by mass.
[3] The filler (d) includes a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less and/or a filler (d-iii) having an average particle size of more than 1 μm and 10 μm or less, in [2] A dental filling kit as described.
[4] The filler (d-ii) and/or the filler (d-iii) contains an inorganic filler containing a silicon atom and/or an inorganic filler composed of an oxide of a silicon atom, and the inorganic filler is The dental filling kit according to [3], which has hydroxyl groups on its surface, and the hydroxyl groups are surface-treated with a surface treatment agent.
[5] The filler (d) is a combination (I) of a filler (d-i) having an average particle size of 1 nm or more and less than 0.1 μm and a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less. , a combination (II) of a filler (d-i) having an average particle diameter of 1 nm or more and less than 0.1 μm and a filler (d-iii) having an average particle diameter of more than 1 μm and 10 μm or less (II), an average particle diameter of 1 nm or more and less than 0.1 μm A combination (III) of a filler (di), a filler (d-ii) having an average particle diameter of 0.1 μm or more and 1 μm or less and a filler (d-iii) having an average particle diameter of more than 1 μm and 10 μm or less, and an average particle The dental filling kit according to any one of [2] to [4], which contains at least one combination selected from the group consisting of combinations (IV) of fillers (d-ii) having a diameter of 0.1 μm or more and 1 μm or less. .
[6] The dental filling kit according to any one of [1] to [5], wherein the glass ionomer cement (Y) further contains a monomer (i) and a photopolymerization initiator (j).
[7] The dental filling kit according to any one of [1] to [6], wherein the self-adhesive dental composite resin (X) is in one dosage form.
[8] Any one of [1] to [7], wherein the content of the fluoroaluminosilicate glass powder (f) is 25 to 85 parts by mass with respect to the total amount of 100 parts by mass of the glass ionomer cement (Y). dental filling kit.
[9] The self-adhesive dental composite resin (X) is for direct sealing of the whole or a part of the cavity, and the glass ionomer cement (Y) is the surface to which the self-adhesive dental composite resin (X) is applied. The dental filling kit according to any one of [1] to [8], which is for covering the
[10] applying a self-adhesive dental composite resin (X) to a predetermined area of the tooth; and glass ionomer cement (Y) to the predetermined area to which the self-adhesive dental composite resin (X) has been applied. and applying
The self-adhesive dental composite resin (X) comprises a monomer having an acidic group (a), a monomer having no acidic group (b), and a photopolymerization initiator (c),
A method for restoring teeth, wherein the glass ionomer cement (Y) contains a fluoroaluminosilicate glass powder (f), a polycarboxylic acid-based polymer (g), and water (h).

According to the present invention, by filling the cavity with a self-adhesive dental composite resin and then filling the upper portion with a glass ionomer cement, excellent cavity sealing properties and adhesion to the tooth substance can be achieved by a simple method. A dental filling kit can be provided that exhibits robustness. Moreover, according to the present invention, it is possible to provide a dental filling kit having excellent ion releasing properties. Furthermore, according to the present invention, it is possible to provide a dental filling kit that does not require processes such as the use of conditioners and bonding materials, can be used simply, and has excellent operability.

FIG. 3 is a schematic cross-sectional view showing an example of filling of the dental filling kit of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of filling of the dental filling kit of the present invention.

The dental filling kit of the present invention comprises a self-adhesive dental composite resin (X) and a glass ionomer cement (Y). The self-adhesive dental composite resin (X) contains a monomer having an acidic group (a), a monomer having no acidic group (b), and a photopolymerization initiator (c). The content of the monomer (a) having an acidic group in the self-adhesive dental composite resin (X) is 1 to 30 mass parts per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). Department. Glass ionomer cement (Y) contains fluoroaluminosilicate glass powder (f), polycarboxylic acid polymer (g), and water (h).

In this specification, "(meth)acrylic" is a generic term for methacrylic and acryl, and the same applies to similar expressions ("(meth)acrylic acid", "(meth)acrylonitrile", etc.). 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.

Although the reason why the dental filling kit of the present invention exhibits excellent cavity sealing properties with a simple method is not clear, it is presumed as follows. That is, in order to exhibit excellent cavity sealing properties, the method of filling the cavity with the glass ionomer cement (Y) is not limited to only partially adhering the composite resin and the dentin (for example, only at the enamel portion). , may not be sufficient. Since the self-adhesive dental composite resin (X) provided in the dental filling kit of the present invention is also excellent in adhesiveness to dentin (especially dentin), With the self-adhesive dental composite resin (X) in the cavity, it is possible to seal the cavity with the self-adhesive dental composite resin (X) not only at the margin but also at the side and the cavity bottom. there is Furthermore, due to the exposed portion of the glass ionomer cement on the surface of the cavity, ion releasing properties can also be expected.

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

First, the self-adhesive dental composite resin (X) will be described.

<monomer>
A radical monomer is preferably used as the monomer used in the self-adhesive dental composite resin (X) of the present invention. Specific examples of radical monomers in monomers include (meth)acrylate-based monomers, (meth)acrylamide-based monomers, α-cyanoacrylic acid, (meth)acrylic acid, and α-halogenated acrylic acid. , esters such as crotonic acid, cinnamic acid, sorbic acid, maleic acid and itaconic acid, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. Among these, (meth)acrylate-based monomers and (meth)acrylamide-based monomers are preferred from the viewpoint of curability. Furthermore, from the viewpoint of adhesiveness to tooth substance and elastic modulus, the monomers in the self-adhesive dental composite resin (X) of the present invention are the monomer (a) having an acidic group and the monomer (a) having an acidic group. It is necessary to contain a monomer (b) that does not

<Monomer (a) having an acidic group>
As the monomer (a) having an acidic group used in the present invention, for example, at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, a sulfonic acid group, etc. A unique monomer can be mentioned. The monomer (a) having an acidic group can be used singly or in an appropriate combination of two or more. Specific examples of the monomer (a) having an acidic group are given below.

Examples of monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyloxybutyldihydrogenphosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) acryloyloxyoctyl dihydrogen Phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydecyl Dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth) acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[ 4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth) acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyloxyethylphenyl hydrogen Phosphate, 2-(meth)acryloyloxyethyl-(2-bromoethyl) hydrogen phosphate, 2-methacryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl-(4-methoxyphenyl) hydrogen Phosphates and their acid chlorides, alkali metal salts and amine salts are included.

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 amine salts thereof.

Monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogen Thiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth) Acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydrogenthiophosphate Phosphate, 12-(meth)acryloyl oxide decyl dihydrogenthiophosphate, 16-(meth) acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth) acryloyloxyicosyl dihydrogenthiophosphate and acid salts thereof substances, alkali metal salts, and ammonium salts.

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.

As the monomer having a carboxylic acid group, a monofunctional (meth)acrylic acid ester having one carboxyl group or its acid anhydride group in the molecule, multiple carboxyl groups or its acid anhydride group in the molecule and monofunctional (meth) acrylic acid esters having

Examples of monofunctional monomers having one carboxyl group or its acid anhydride group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth) acryloyloxyethyl hydrogen succinate, 2-(meth) acryloyloxyethyl hydrogen phthalate, 2-(meth) acryloyloxyethyl hydrogen malate, O-(meth) acryloyl tyrosine, N-(meth) Acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-( meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, etc. and the carboxyl groups of these compounds Compounds with anhydride groups can be mentioned.

Examples of monofunctional monomers having multiple carboxyl groups or acid anhydride groups thereof in the molecule include, for example, 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyl Oxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydecane -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, 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic anhydride, 6-(meth)acryloyloxy Ethylnaphthalene-2,3,6-tricarboxylic anhydride, 4-(meth)acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4-(meth)acryloyloxyethylnaphthalene-1,8- tricarboxylic acid anhydride and the like.

Examples of monomers having a sulfonic acid group include 2-sulfoethyl (meth)acrylate and the like.

Among the above monomers (a) having an acidic group, monomers having a phosphoric acid group or carboxylic acids are preferred from the viewpoint of good adhesive strength when used as a self-adhesive dental composite resin (X). It preferably contains a monomer having an acid group, such as 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) acryloyloxyoctyl dihydrogen phosphate hydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, 11-(meth)acryloyloxyundecyldihydrogenphosphate, 12-(meth)acryloyl Oxidodecyl dihydrogen phosphate, 16-(meth) acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth) acryloyloxyicosyl dihydrogen phosphate, 4-(meth) acryloyloxyethyl trimellitate anhydride, 4 -(meth)acryloyloxyethyl trimellitate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl) hydrogen phosphate 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth) acryloyloxyundecyl dihydrogen phosphate, 12-(meth) acryloyl oxide decyl dihydrogen phosphate, 16-(meth) acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth) acryloyloxyicosyl dihydrogen phosphate More preferably, from the viewpoint of balance with curability, 10-(meth) acryloyloxy Sidecyl dihydrogen phosphate is most preferred.

The content of the monomer (a) having an acidic group in the self-adhesive dental composite resin (X) of the present invention is defined by the content relative to the total amount of the monomers, so that the effect of the present invention can be achieved. is particularly important for From the viewpoint of achieving both adhesion to glass ionomer cement (Y) and adhesion to tooth substance (especially dentin), the content of monomer (a) having an acidic group is the total amount of monomers. In 100 parts by mass, it is necessary to be 1 to 30 parts by mass, preferably 1 to 29 parts by mass, more preferably 2.5 to 27.5 parts by mass, and 5 to 25 parts by mass. is more preferable. When the content of the monomer (a) having an acidic group exceeds 30 parts by mass, the adhesiveness to dentin is reduced.

<Monomer (b) having no acidic group>
The monomer (b) having no acidic group in the present invention includes an asymmetric acrylamide/methacrylic acid ester compound (b-1); Hydrophobic monomer (b-2) (hereinafter sometimes simply referred to as “hydrophobic monomer (b-2)”); does not have an acidic group having a solubility in water at 25° C. of 10 g/L or more Hydrophilic monomer (b-3) (hereinafter sometimes simply referred to as "hydrophilic monomer (b-3)"). The monomer (b) having no acidic group may be used alone or in combination of two or more. In the present invention, a compound having no acidic group and containing an acrylamide group and a methacryloyloxy group is defined as an asymmetric acrylamide/methacrylic acid ester compound (b-1). Compounds not included in the methacrylic acid ester compound (b-1) are divided into hydrophobic monomers (b-2) and hydrophilic monomers (b-3) according to the degree of hydrophilicity.

- Asymmetric acrylamide/methacrylic acid ester compound (b-1)
A preferred embodiment includes a dental filling kit comprising a self-adhesive dental composite resin (X) containing an asymmetric acrylamide/methacrylate compound (b-1). The asymmetric acrylamide/methacrylic acid ester compound (b-1) improves the adhesion of the self-adhesive dental composite resin (X) to dentin, and is therefore a compound represented by the following general formula (1). is preferably

式中、Ｚは置換基を有していてもよいＣ₁～Ｃ₈の直鎖状又は分岐鎖状の脂肪族基又は芳香族基であって、前記脂肪族基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＮＲ¹－、－ＣＯ－ＮＲ¹－、－ＮＲ¹－ＣＯ－、－ＣＯ－Ｏ－ＮＲ¹－、－Ｏ－ＣＯ－ＮＲ¹－及び－ＮＲ¹－ＣＯ－ＮＲ¹－からなる群より選ばれる少なくとも１個の結合基によって中断されていてもよい。Ｒ¹は、水素原子又は置換基を有していてもよいＣ₁～Ｃ₈の直鎖状若しくは分岐鎖状の脂肪族基を表す。

In the formula, Z is an optionally substituted C ₁ to C ₈ linear or branched aliphatic or aromatic group, wherein the aliphatic group is —O—, — S—, —CO—, —CO—O—, —O—CO—, —NR ^{1 —, —CO—NR 1 —, —NR 1 —CO—, —CO—O—NR 1 — , —O—} It may be interrupted by at least one linking group selected from the group consisting of CO--NR ¹ -- and --NR ¹ --CO--NR ¹ --. R ¹ represents a hydrogen atom or an optionally substituted C ₁ -C ₈ linear or branched aliphatic group.

Z is a site that adjusts the hydrophilicity of the asymmetric acrylamide/methacrylic acid ester compound (b-1). The optionally substituted C ₁ to C ₈ aliphatic group represented by Z is a saturated aliphatic group (alkylene group, cycloalkylene group (eg, 1,4-cyclohexylene group, etc.)) , an unsaturated aliphatic group (alkenylene group, alkynylene group), preferably a saturated aliphatic group (alkylene group) from the viewpoint of availability or ease of production and chemical stability. Z is preferably a linear or branched C ₁ to C ₄ aliphatic group which may have a substituent, from the viewpoint of adhesiveness to dentin and polymerization curability. It is more preferably a linear or branched C ₂ -C ₄ aliphatic group which may have As the aliphatic group, an alkylene group is preferred. Examples of the C ₁ -C ₈ alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group and the like.

The optionally substituted aromatic group represented by Z includes, for example, an aryl group and an aromatic heterocyclic group. As the aromatic group, an aryl group is more preferable than an aromatic heterocyclic group. The heterocyclic ring in the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5- or 6-membered ring. As the aryl group, for example, a phenyl group is preferable. Examples of aromatic heterocyclic groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, triazole, pyran, and pyridine. groups, pyridazine groups, pyrimidine groups, pyrazine groups, and 1,3,5-triazine groups. Among the aromatic groups, a phenyl group is particularly preferred.

The aliphatic group for R ¹ may be either a saturated aliphatic group (alkyl group) or an unsaturated aliphatic group (alkenyl group, alkynyl group). From the viewpoint, it is preferably a saturated aliphatic group (alkyl group). Examples of the C ₁ to C ₈ linear or branched alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2- dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group and the like, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group and the like are preferred.

R ¹ is more preferably a hydrogen atom or an optionally substituted linear or branched C ₁ to C ₄ alkyl group, and a hydrogen atom or an optionally substituted linear alkyl group. Chain or branched C ₁ -C ₃ alkyl groups are more preferred.

When the aliphatic group of Z is interrupted by the linking group, the number of linking groups is not particularly limited, but may be about 1 to 10, preferably 1, 2 or 3. , more preferably one or two. In the above formula (1), the aliphatic group of Z is preferably not interrupted by the continuous bonding groups. That is, it is preferable that the bonding groups are not adjacent to each other. As the binding group, -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, -CO-O- At least one bonding group selected from the group consisting of NH-, -O-CO-NH- and -NH-CO-NH- is preferred, and -O-, -S-, -CO-, -NH-, - At least one linking group selected from the group consisting of CO--NH-- and --NH--CO-- is more preferred.

Substituents for Z include halogen atoms (fluorine, chlorine, bromine and iodine atoms), carboxyl groups, C ₂ to C ₆ linear or branched acyl groups, C ₁ to C ₆ linear A chain or branched alkyl group, a C ₁ to C ₆ linear or branched alkoxy group, and the like can be mentioned.

Specific examples of the asymmetric acrylamide/methacrylic acid ester compound (b-1) include, but are not particularly limited to, those shown below.

Among them, from the viewpoint of adhesiveness to tooth substance and polymerization curability, asymmetric acrylamide, wherein Z is a linear or branched aliphatic group of C ₂ to C ₄ optionally having a substituent group. Methacrylic acid ester compounds are preferred, and N-methacryloyloxyethylacrylamide (commonly known as "MAEA"), N-methacryloyloxypropylacrylamide, N-methacryloyloxybutylacrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide , N-(2-(2-methacryloyloxyethoxy)ethyl)acrylamide are more preferable, and MAEA and N-methacryloyloxypropylacrylamide are more preferable from the viewpoint of high hydrophilicity related to penetration into the collagen layer of dentin.

The asymmetric acrylamide/methacrylic acid ester compound (b-1) may be used singly or in combination of two or more. The content of the asymmetric acrylamide/methacrylic acid ester compound (b-1) is not particularly limited as long as the effect of the present invention is exhibited. The parts by mass are preferably 1 to 60 parts by mass, more preferably 2 to 45 parts by mass, still more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass.

- Hydrophobic monomer having no acidic group (b-2)
A preferred embodiment includes a dental filling kit comprising a self-adhesive dental composite resin (X) containing a hydrophobic monomer (b-2) having no acidic group. The hydrophobic monomer (b-2) having no acidic group improves the handleability of the self-adhesive dental composite resin (X) and the mechanical strength of the cured product. The hydrophobic monomer (b-2) is preferably a radical monomer having a polymerizable group without an acidic group, and from the viewpoint of facilitating radical polymerization, the polymerizable group is a (meth)acrylic group and / or (meth) acrylamide groups are preferred. The hydrophobic monomer (b-2) has no acidic group, does not correspond to the asymmetric acrylamide/methacrylate compound (b-1), and has a solubility in water at 25°C of less than 10 g/L. means a monomer of Examples of the hydrophobic monomer (b-2) include, for example, aromatic compound-based bifunctional monomers, aliphatic compound-based bifunctional monomers, trifunctional or higher monomers, and the like. monomers of the same type.

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)acryloyloxydipropoxyphenyl) 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 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”), 1,10-decanediol dimethacrylate (commonly known as “DD”), 2,2,4-trimethylhexamethylenebis (2-Carbamoyloxyethyl) dimethacrylate is preferred.

Tri- or higher functional monomers include, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth) Acrylate, 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 (b-2), from the viewpoint of mechanical strength and handling properties, aromatic compound-based bifunctional monomers and aliphatic compound-based bifunctional monomers are preferred. It is preferably used. Bis-GMA and D-2.6E are preferable as the aromatic compound-based bifunctional monomer. Aliphatic compound-based bifunctional monomers include glycerol di(meth)acrylate, 3G, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, DD, 1,2- Bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, UDMA is preferred.

Among the above hydrophobic monomers (b-2), Bis-GMA, D-2.6E, 3G, UDMA and DD are more preferred, and D-2.6E, 3G and Bis-GMA are even more preferred.

The hydrophobic monomer (b-2) may be blended singly or in combination of two or more. The content of the hydrophobic monomer (b-2) in the self-adhesive dental composite resin (X) of the present invention is preferably 20 to 98 parts by mass, more preferably 40 to 95 parts by mass, based on 100 parts by mass of the total amount of monomers. Parts by weight are more preferred, and 60 to 92 parts by weight are even more preferred. When the content of the hydrophobic monomer (b-2) is equal to or less than the following upper limit, the wettability of the self-adhesive dental composite resin (X) to tooth structure is reduced, resulting in a reduction in adhesive strength. is easily suppressed, and when the content is at least the lower limit, the desired mechanical strength of the cured product can be easily obtained.

- Hydrophilic monomer having no acidic group (b-3)
In a preferred embodiment, the monomer (b) having no acidic group contains a hydrophilic monomer (b-3) having no acidic group, a self-adhesive dental composite resin. A dental filling kit comprising (X) is included. The hydrophilic monomer (b-3) improves the wettability of the self-adhesive dental composite resin (X) to tooth substance. The hydrophilic monomer (b-3) is preferably a radical monomer having a polymerizable group without an acidic group, and from the viewpoint of facilitating radical polymerization, the polymerizable group is a (meth) acrylic group and / or (meth) acrylamide groups are preferred. The hydrophilic monomer (b-3) has no acidic group, does not correspond to the asymmetric acrylamide/methacrylate compound (b-1), and has a water solubility of 10 g/L or more at 25°C. is preferably a monomer having a solubility of 30 g/L or more, and more preferably a monomer that is soluble in water at an arbitrary ratio at 25°C. As the hydrophilic monomer, those having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group and an amide group are preferred. Examples of the hydrophilic monomer (b-3) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) ) acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups), etc. monofunctional (meth)acrylate monomers; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis (2-hydroxyethyl) (meth)acrylamide, N-methoxy methyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl (meth)acrylamide, N,N-dimethylacrylamide and Examples include monofunctional (meth)acrylamide-based monomers such as N,N-diethylacrylamide.

Among these hydrophilic monomers (b-3), 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, diacetone (meth)acrylamide and Hydrophilic monofunctional (meth)acrylamide-based monomers are preferred, and 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide and N,N-diethylacrylamide are more preferred. The hydrophilic monomer (b-3) may be blended singly or in combination of two or more.

The content of the hydrophilic monomer (b-3) in the self-adhesive dental composite resin (X) of the present invention is preferably in the range of 0 to 50 parts by mass with respect to 100 parts by mass of the total amount of monomers. 40 parts by mass is more preferable, and 0 to 30 parts by mass is even more preferable. The content of the hydrophilic monomer (b-3) may be 0 parts by mass with respect to 100 parts by mass of the total amount of the monomers. When the content of the hydrophilic monomer (b-3) in the self-adhesive dental composite resin (X) of the present invention is at least the above lower limit, a sufficient effect of improving adhesive strength can be easily obtained, and the above upper limit is easily obtained. By being below the value, it is easy to obtain the desired mechanical strength of the cured product.

The content of the monomer (b) having no acidic group in the self-adhesive dental composite resin (X) is 60 to 60 parts per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). 99 parts by mass is preferable, 65 to 97 parts by mass is more preferable, and 70 to 95 parts by mass is even more preferable. From the viewpoint of adhesiveness to tooth substance, the mass ratio ((b-2):(b-3)) of the hydrophobic monomer (b-2) and the hydrophilic monomer (b-3) is 10:0. ~1:2 is preferred, 10:0 to 1:1 is more preferred, and 10:0 to 2:1 is even more preferred.

A preferred embodiment includes a self-adhesive dental composite resin (X) substantially free of bifunctional or higher (meth)acrylamide-based monomers. Another preferred embodiment includes a self-adhesive dental composite resin (X) substantially free of trifunctional or higher (meth)acrylamide-based monomers. Another preferred embodiment is a self-adhesive dental composite resin (X) that is substantially free of hydrogen phosphate diester group-containing monomers. The hydrogen phosphate diester group-containing monomer preferably has a (meth)acryloyloxy group and/or a (meth)acrylamide group. In the present invention, "substantially free of a certain monomer" means that the content of the monomer is 0 in the total amount of 100 parts by mass of the monomers contained in the self-adhesive dental composite resin (X). It is less than 0.5 part by mass, preferably less than 0.1 part by mass, more preferably less than 0.01 part by mass, and may be 0 part by mass. In addition, the content of the monomer that is not substantially contained may be less than 0.5% by mass, or less than 0.1% by mass, in the entire self-adhesive dental composite resin (X). may

Another preferred embodiment includes a self-adhesive dental composite resin (X) that is substantially free of (meth)acrylic block copolymers. The (meth)acrylic block copolymer may have a molecular weight distribution (weight average molecular weight/number average molecular weight) of, for example, 1.02 to 2.00. The molecular weight distribution can be measured by a known method, for example, gel permeation chromatography (GPC), and calculated as a standard polystyrene-equivalent value. The (meth)acrylic block copolymer may be bifunctional or higher or tetrafunctional or higher.

<Photoinitiator (c)>
The photopolymerization initiator (c) is classified into a water-soluble photopolymerization initiator (c-1) and a water-insoluble photopolymerization initiator (c-2). As the photopolymerization initiator (c), only the water-soluble photopolymerization initiator (c-1) may be used, or only the water-insoluble photopolymerization initiator (c-2) may be used. The photopolymerization initiator (c-2) and the water-insoluble photopolymerization initiator (c-2) may be used in combination, but are preferably used in combination.

- Water-soluble photopolymerization initiator (c-1)
The water-soluble photopolymerization initiator (c-1) can improve the polymerization curability at the hydrophilic tooth surface interface and realize high adhesive strength. The water-soluble photopolymerization initiator (c-1) has a solubility in water at 25° C. of 10 g/L or more, preferably 15 g/L or more, more preferably 20 g/L or more, and 25 g/L or more. L or more is more preferable. When the solubility is 10 g/L or more, the water-soluble photopolymerization initiator (c-1) is sufficiently dissolved in the water in the dentin at the adhesive interface, and the effect of promoting polymerization is easily exhibited.

Water-soluble photopolymerization initiators (c-1) include, for example, water-soluble thioxanthones, water-soluble acylphosphine oxides, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl -1-Propan-1-one in which a (poly)ethylene glycol chain is introduced into the hydroxyl group, 1-hydroxycyclohexylphenylketone in which a (poly)ethylene glycol chain is introduced into the hydroxyl group and/or the phenyl group, 1-hydroxy -OCH ₂ COO ^- Na ⁺ is introduced into the phenyl group of cyclohexylphenyl ketone, and (poly)ethylene glycol chain is introduced into the hydroxyl group and/or phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one. α-hydroxyalkylacetophenones, such as those introduced with —OCH ₂ COO ⁻ Na ⁺ into the phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one; 2-methyl-1[ α-Aminoalkylphenones such as 4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone A quaternary ammonium salt of the amino group of is mentioned.

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.

Examples of the water-soluble acylphosphine oxides include acylphosphine oxides represented by the following general formula (2) or (3).

In formulas (2) and (3), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a C ₁ to C ₄ linear or branched alkyl group; or a halogen atom, and 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 ⁺ R ⁹ R ¹⁰ R ¹¹ (wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently an organic group or a hydrogen atom), n is 1 or 2, and X is a straight C ₁ to C ₄ It is a chain or branched alkylene group, R ⁸ is —CH(CH ₃ )COO(C ₂ H ₄ O) _p CH ₃ , and p is an integer of 1-1,000.

The alkyl groups for R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are not particularly limited as long as they are C ₁ to C ₄ linear or branched alkyl groups. ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group and the like. The alkyl group for R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably a C ₁ to C ₃ linear alkyl group, more preferably a methyl group or an ethyl group, and a methyl group. is more preferred. Examples of X include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group and the like. X is preferably a C ₁ to C ₃ linear alkylene group, more preferably a methylene group or an ethylene group, and still more preferably a methylene group.

When M is a pyridinium ion, the substituents on the pyridine ring include halogen atoms (fluorine, chlorine, bromine, and iodine atoms), carboxyl groups, and C ₂ to C ₆ linear or branched acyl groups. C ₁ to C ₆ linear or branched alkyl groups, C ₁ to C ₆ linear or branched alkoxy groups, and the like. 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 ⁺ R ⁹ R ¹⁰ R ¹¹ (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 for R ⁹ , R ¹⁰ and R ¹¹ include the same substituents for the pyridine ring (excluding halogen atoms).

Among these, compounds in which R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are all methyl groups are particularly preferred from the viewpoint of storage stability and color tone stability in the composition. Ammonium ions include ammonium ions 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.

As R8, from the viewpoint of adhesiveness, p is preferably ¹ or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 4 or more, preferably 1000 or less, more preferably 100 or less, and 75 or less. More preferably, 50 or less is particularly preferable.

Among these water-soluble acylphosphine oxides, the compound represented by the general formula (2), in which M ⁿ⁺ is a lithium ion, and the portion corresponding to the group represented by R ⁸ have a molecular weight of Compounds represented by the general formula (3) synthesized from polyethylene glycol methyl ether methacrylate of 950 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. The water-soluble photopolymerization initiator (c-1) may be used alone or in combination of two or more.

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

When the water-soluble photopolymerization initiator (c-1) is dispersed as a powder, if the average particle size of the powder is too large, it tends to settle, so the average particle size is preferably 500 μm or less, and 100 μm or less. is more preferably 50 μm or less. On the other hand, if the average particle size of the powder 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 (c-1) is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.01 to 100 μm, and 0.01 to 50 μm. is more preferably in the range of

The average particle size of the powder of the water-soluble photopolymerization initiator (c-1) is determined using image analysis type particle size distribution measurement 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 image analysis is performed by

When the water-soluble photopolymerization initiator (c-1) is dispersed as a powder, the shape of the water-soluble photopolymerization initiator (c-1) may be spherical, needle-like, plate-like, or crushed. Examples include, but are not particularly limited to. The water-soluble photopolymerization initiator (c-1) can be prepared by a conventionally known method such as a pulverization method, a freeze-drying method, and a reprecipitation method. and reprecipitation methods are preferred, and freeze-drying methods are more preferred.

From the viewpoint of the curability of the self-adhesive dental composite resin (X), the content of the water-soluble photopolymerization initiator (c-1) is less than the amount of the monomer in the self-adhesive dental composite resin (X). The total amount is 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass from the viewpoint of adhesion to tooth substance. When the content of the water-soluble photopolymerization initiator (c-1) is at least the above lower limit, polymerization at the adhesive interface proceeds sufficiently, and sufficient adhesive strength can be easily obtained. On the other hand, when the content of the water-soluble photopolymerization initiator (c-1) is equal to or less than the upper limit, sufficient adhesive strength can be easily obtained.

- Water-insoluble photopolymerization initiator (c-2)
In the self-adhesive dental composite resin (X) of the present invention, from the viewpoint of curability, the water-insoluble photopolymerization initiator (c-1) has a solubility in water at 25°C of less than 10 g/L. It preferably contains a soluble photopolymerization initiator (c-2) (hereinafter sometimes referred to as a water-insoluble photopolymerization initiator (c-2)). A known water-insoluble photopolymerization initiator can be used as the water-insoluble photopolymerization initiator (c-2) used in the present invention. The water-insoluble photopolymerization initiator (c-2) may be blended alone or in combination of two or more.

Examples of the water-insoluble photopolymerization initiator (c-2) include (bis)acylphosphine oxides other than the water-soluble photopolymerization initiator (c-1), thioxanthones, ketals, α-diketones, coumarins, Examples include anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds.

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.

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, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenequinone, and the like. is mentioned. Among these, dl-camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

Examples of the coumarins include 3,3′-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3 -benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p- nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 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. JP-A-9-3109 Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 10-245525.

Among the above coumarins, 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 photopolymerization initiators (c-2), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins. As a result, a self-adhesive dental composite resin ( X) is obtained.

The content of the water-insoluble photopolymerization initiator (c-2) is not particularly limited. It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and further 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of monomers in the dental composite resin (X). preferable. In addition, since the content of the water-insoluble photopolymerization initiator (c-2) is equal to or less than the above upper limit, even when the polymerization performance of the water-insoluble photopolymerization initiator (c-2) itself is low, it is sufficiently A good adhesive strength can be easily obtained, and precipitation of the water-insoluble photopolymerization initiator (c-2) itself from the self-adhesive dental composite resin (X) can be suppressed.

When a water-soluble photopolymerization initiator (c-1) and a water-insoluble photopolymerization initiator (c-2) are used in combination, the water-soluble photopolymerization initiator (c-1) and water-insoluble photopolymerization in the present invention The mass ratio [(c-1):(c-2)] of the initiator (c-2) is preferably 10:1 to 1:10, more preferably 7:1 to 1:7, More preferably 5:1 to 1:5, particularly preferably 3:1 to 1:3. When the water-soluble photopolymerization initiator (c-1) is contained in a mass ratio of more than 10:1, the curability of the self-adhesive dental composite resin (X) itself is lowered, resulting in high adhesive strength. can be difficult. On the other hand, when the water-insoluble photopolymerization initiator (c-2) is contained in a mass ratio of more than 1:10, the curability of the self-adhesive dental composite resin (X) itself is enhanced, but the adhesion interface is polymerized. Promotion may be insufficient and it may be difficult to develop high bond strength.

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

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, Examples include inorganic fillers containing silicon atoms such as silica-coated ytterbium fluoride and inorganic fillers composed of oxides. These may also be used individually by 1 type, and can be used in mixture of 2 or more types. Among these, quartz, silica, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride are preferable in terms of excellent mechanical strength and transparency of the resulting self-adhesive dental composite resin (X). More preferred are quartz, silica, silica-zirconia, barium glass, and silica-coated ytterbium fluoride. From the viewpoint of handling property and mechanical strength of the resulting self-adhesive dental composite resin (X), the inorganic filler preferably has an average particle size of 0.001 to 50 μm, more preferably 0.001 to 10 μm. is more preferable. In the present invention, 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. A preferred embodiment includes a self-adhesive dental composite resin (X) in which the filler (d) is an inorganic filler.

In another preferred embodiment, the filler (d) of the self-adhesive dental composite resin (X) is a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less (hereinafter simply referred to as “filler ( d-ii)”) and / or a filler (d-iii) with an average particle size of more than 1 μm and 10 μm or less (hereinafter simply referred to as “filler (d-iii)”), dental Filling kits are included. When the filler (d) of the self-adhesive dental composite resin (X) contains the filler (d-ii) and/or the filler (d-iii), a predetermined content of the monomer (a) having an acidic group , and optionally in combination with other configurations, provide better adhesion to dentin and better cavity sealing. In another preferred embodiment, the filler (d) of the self-adhesive dental composite resin (X) comprises a filler (d-ii) and/or a filler (d-iii), and the filler (d -ii) and/or the filler (d-iii) contains an inorganic filler composed of an inorganic filler or an oxide containing a silicon atom, the inorganic filler has a hydroxyl group on the surface, and the hydroxyl group is a surface treatment A dental filling kit, which is surface-treated with an agent, can be mentioned. When the self-adhesive dental composite resin (X) contains an inorganic filler surface-treated with a surface-treating agent, the monomer (a) having an acidic group has a predetermined content and, if necessary, other constitutions. When combined, a better adhesion to the dentin and a better cavity sealing property are obtained, and the self-adhesive dental composite resin (X) is applied to the cavity bottom with the glass ionomer cement (Y). Superior ion release is obtained when applied prior to In any of the preferred embodiments described above, the filler (d) of the self-adhesive dental composite resin (X) comprises a filler (di) having an average particle size of 1 nm or more and less than 0.1 μm, which will be described later, and an average particle A combination (I) with a filler (d-ii) having a diameter of 0.1 μm or more and 1 μm or less, a filler (d-i) 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 (d Combination (II) with -iii) and combination (IV) with filler (d-ii) are preferred, and combinations (I) and (II) are particularly preferred.

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 cured product of the self-adhesive dental composite resin (X), it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler refers to particles observed in a unit field of view taken by taking a photograph of the filler with an electron microscope. It is a filler having a degree of 0.6 or more. The average particle size of the spherical filler is preferably 0.05-5 μm. When the average particle size is at least the above lower limit, the self-adhesive dental composite resin (X) is likely to have a sufficient filling rate of the spherical filler and a desired mechanical strength. On the other hand, when the average particle size is equal to or less than the upper limit, the surface area of the spherical filler is less likely to decrease, and a cured product of the self-adhesive dental composite resin (X) having desired mechanical strength can be easily obtained.

In order to adjust the fluidity of the self-adhesive dental composite resin (X), 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 surface treatment agent, it is possible to obtain an inorganic filler in which the hydroxyl groups are surface-treated. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11 -methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like.

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 to the inorganic filler described above, making it into a paste, polymerizing it, and pulverizing it. The organic-inorganic composite filler indicates a filler containing an inorganic filler and a polymer of polymerizable monomers. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler are mixed, polymerized and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. The organic-inorganic composite fillers may also be used singly or in combination of two or more. From the viewpoint of handling property and mechanical strength of the composition of self-adhesive dental composite resin (X) obtained, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm. It is more preferably 0.001 to 10 μm.

Materials for organic fillers include, for example, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. , chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. 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 viewpoint of handling property and mechanical strength of the resulting self-adhesive dental composite resin (X), the average particle size of the organic filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. It is more preferable to have

In addition, in this specification, the average particle size of the filler 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, the 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). be able to.

Specifically, for example, electron microscopic observation is performed by taking a photograph of particles with an electron microscope (manufactured by Hitachi, Ltd., S-4000 type), and measuring the particle diameter of the particles (200 or more) observed in the unit field of view of the photograph. , image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountec Co., Ltd.)). At this time, the particle diameter 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 self-adhesive dental composite resin (X) of the present invention, it is preferable to use two or more fillers having different materials, particle size distributions and morphologies in combination or in combination. By combining two or more types of fillers, the fillers are densely packed and the number of interaction points between the fillers and the monomer or between the fillers increases. Also, depending on the type of filler, it is possible to control the fluidity of the paste depending on the presence or absence of shear force. 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 (d) is a filler (di) having an average particle size of 1 nm or more and less than 0.1 μm, Combination (I) with a filler (d-ii) having an average particle diameter of 0.1 μm or more and 1 μm or less, a filler (d-i) 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 (d-iii), filler (d-i) having an average particle size of 1 nm or more and less than 0.1 μm, filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less, average particle size A combination (III) with a filler (d-iii) of more than 1 μm and 10 μm or less, and a combination (IV) of a filler (d-ii) having an average particle diameter of 0.1 μm or more and 1 μm or less are preferable. Among these combinations, From the viewpoint of paste properties and cavity sealing properties, (I), (II) and (III) are more preferred, and (I) and (II) are more preferred. The combination (IV) of fillers (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less is an embodiment containing two types of fillers (d-ii) 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 (d) of each particle diameter may contain a different kind of filler. 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 (d) is not particularly limited, but from the viewpoint of the mechanical strength of the cured product and the adhesiveness to the tooth substance, it is 50 to 90 parts by mass in the total amount of 100 parts by mass of the self-adhesive dental composite resin (X). parts, more preferably 55 to 85 parts by mass, even more preferably 60 to 80 parts by mass.

The method for producing a self-adhesive dental composite resin (X) contains the above components, and the content of the monomer (a) having an acidic group is 1 to 30 parts by mass in 100 parts by mass of the total amount of monomers. There is no particular limitation as long as the content of the filler (d) is 50 to 90 parts by mass in 100 parts by mass of the total amount of the self-adhesive dental composite resin (X). It can be manufactured easily.

<Polymerization accelerator (e)>
The self-adhesive dental composite resin (X) contains a water-soluble photopolymerization initiator (c-1) or a water-insoluble photopolymerization initiator (c-2) and/or a polymerization accelerator together with a chemical polymerization initiator described later. (e) can be used. The polymerization accelerator (e) used in the present invention includes, for example, amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes , thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, and the like.

Amines used as the polymerization accelerator (e) are classified into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, tertiary aliphatic amines are preferred from the viewpoint of curability and storage stability of the self-adhesive dental composite resin (X), and among these, N-methyldiethanolamine and triethanolamine are 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-diisopropylaniline, 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)benzoic acid methyl, 4-(N,N-dimethylamino)propyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 4-(N,N-dimethylamino)benzoate 2-(methacryloyloxy ) ethyl, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-dimethylamino)butyl benzoate and the like. Among these, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethylamino ) At least one selected from the group consisting of ethyl benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate 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.

The polymerization accelerator (e) may contain one type alone, or may contain two or more types in combination. The content of the polymerization accelerator (e) used in the present invention is not particularly limited, but from the viewpoint of the curability of the resulting self-adhesive dental composite resin (X ) is preferably from 0.001 to 30 parts by mass, more preferably from 0.01 to 10 parts by mass, and even more preferably from 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the monomers. When the content of the polymerization accelerator (e) is at least the above lower limit, the polymerization proceeds sufficiently, and sufficient adhesive strength can be easily obtained, and it is more preferably at least 0.05 parts by mass. On the other hand, when the content of the polymerization accelerator (e) is equal to or less than the above upper limit, sufficient adhesiveness can be easily obtained, and the polymerization accelerator (e) from the self-adhesive dental composite resin (X) Since the precipitation of itself can be suppressed, it is more preferably 20 parts by mass or less.

<Chemical polymerization initiator>
The self-adhesive dental composite resin (X) 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. One chemical polymerization initiator may be used alone, or two or more thereof may be used in combination.

<Fluoride ion-releasing substance>
The self-adhesive dental composite resin (X) of the present invention may further contain a fluoride ion-releasing substance. A self-adhesive dental composite resin (X) capable of imparting acid resistance to tooth substance is obtained by containing 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 substance may contain one type alone, or may contain two or more types in combination.

Further, the self-adhesive dental composite resin (X) of the present invention may contain known additives within a range that does not impair performance. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, solvents such as organic solvents, and thickeners. An additive may be used individually by 1 type, and may use 2 or more types together. In one embodiment, the solvent (e.g., water, organic solvent) content in the self-adhesive dental composite resin (X) is less than 1% by weight based on the total weight of the self-adhesive dental composite resin (X). is preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass.

Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene and the like. The content of the polymerization inhibitor is preferably 0.001 to 1.0 parts by weight per 100 parts by weight of the monomer (a) of the self-adhesive dental composite resin (X).

Next, the glass ionomer cement (Y) will be explained.

Glass ionomer cement (Y) is a composition containing fluoroaluminosilicate glass powder (f), polycarboxylic acid polymer (g), and water (h).

<Fluoroaluminosilicate glass powder (f)>
As the fluoroaluminosilicate glass powder (f), substances conventionally used in dental cement can be used, and contain Al ³⁺ , Si ⁴⁺ , F−, O ²⁻ as main components, and further Sr ²⁺ and /or Ca ²⁺ -containing fluoroaluminosilicate glass powders are preferred. The content of fluorine (F) in the fluoroaluminosilicate glass powder is preferably 1 to 35% by mass, more preferably 3 to 25% by mass. The content of aluminum in the fluoroaluminosilicate glass powder is preferably 15 to 40% by mass, more preferably 20 to 35% by mass in terms of aluminum oxide (Al ₂ O ₃ ). The content of silicon in the fluoroaluminosilicate glass powder is preferably 15 to 50% by mass, more preferably 20 to 40% by mass in terms of silicon oxide (SiO ₂ ). The content of phosphorus in the fluoroaluminosilicate glass powder is preferably 0 to 15% by mass, more preferably 1 to 7% by mass, in terms of phosphorus (V) oxide (P ₂ O ₅ ). preferable. The content of calcium in the fluoroaluminosilicate glass powder is preferably 0 to 30% by mass, more preferably 1 to 20% by mass in terms of calcium oxide (CaO). The strontium content in the fluoroaluminosilicate glass powder is preferably 0 to 40% by mass, more preferably 10 to 30% by mass in terms of strontium oxide (SrO). The content of the fluoroaluminosilicate glass powder (f) is preferably 25 to 85 parts by mass per 100 parts by mass of the total amount of the glass ionomer cement (Y). When the content of the fluoroaluminosilicate glass powder (f) is at least the lower limit, the strength of the cured product is improved, and when it is at most the upper limit, an increase in viscosity can be suppressed.

<Polycarboxylic acid polymer (g)>
The polycarboxylic acid-based polymer (g) is not particularly limited, but homopolymers or copolymers of α,β-unsaturated carboxylic acids can be used. Examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citracone. acids and the like. The polycarboxylic acid polymer (g) is a copolymer of an α,β-unsaturated carboxylic acid and a monomer capable of copolymerizing with the α,β-unsaturated carboxylic acid. good too. Monomers that can be copolymerized with α,β-unsaturated carboxylic acids include, for example, acrylamide, acrylonitrile, methacrylic acid esters, acrylates, vinyl chloride, allyl chloride, and vinyl acetate. In this case, the ratio of the α,β-unsaturated carboxylic acid to the monomers constituting the polycarboxylic acid polymer is preferably 50% by mass or more. The polycarboxylic acid polymer is preferably a homopolymer or copolymer of acrylic acid or itaconic acid. At least part of the polycarboxylic acid-based polymer may be powder.

A preferred weight average molecular weight of the polycarboxylic acid polymer (g) is in the range of 4,000 to 40,000. When the weight average molecular weight of the polycarboxylic acid-based polymer (g) is 4,000 or more, the strength and durability of the cured product are excellent, and the adhesive strength to tooth substance may be further improved. Further, when the weight average molecular weight is 40,000 or less, the consistency at the time of kneading can be kept in an appropriate range and kneading is easy, which is preferable. The weight average molecular weight means the polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC). Specifically, the following methods are mentioned. Tetrahydrofuran is used as an eluent, and two columns of "TSKgel SuperMultipore HZM-M" manufactured by Tosoh Corporation and "TSKgel SuperHZ4000" connected in series are used as columns. As a GPC apparatus, "HLC-8320GPC" manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) is used. For measurement, 4 mg of sample is dissolved in 5 mL of tetrahydrofuran to prepare a sample solution. Next, the temperature of the column oven is set to 40° C., 20 μL of the sample solution is injected at an eluent flow rate of 0.35 mL/min, and the chromatogram of the sample is measured. On the other hand, 10 points of standard polystyrene having a molecular weight within the range of 400 to 5,000,000 are subjected to GPC measurement to prepare a calibration curve showing the relationship between retention time and molecular weight. Based on this calibration curve, the weight average molecular weight is obtained from the chromatogram of the sample measured as described above.

<Water (h)>
The glass ionomer cement (Y) must contain water (h) for hardening the polycarboxylic acid polymer (g) and the fluoroaluminosilicate glass (f). The content of water (h) in 100 parts by mass of the total amount of glass ionomer cement (Y) is preferably 0.1 to 95 parts by mass, more preferably 0.5 to 90 parts by mass, and even more preferably 1 to 85 parts by mass. . In one embodiment, the content of water (h) in 100 parts by mass of the total amount of glass ionomer cement (Y) may be 1 to 65 parts by mass.

<Monomer (i)>
In a preferred embodiment, the glass ionomer cement (Y) further contains the monomer (i) from the viewpoint of adhesion to the self-adhesive dental composite resin (X) and toughness of the glass ionomer cement (Y). A dental filling kit comprising: A radical monomer is preferably used as the monomer (i). Specific examples of radical monomers in monomer (i) include (meth)acrylate-based monomers, (meth)acrylamide-based monomers, α-cyanoacrylic acid, (meth)acrylic acid, α-halogen esters such as acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid and itaconic acid, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. Among these, (meth)acrylate-based monomers and (meth)acrylamide-based monomers are preferred from the viewpoint of curability. Specific examples of the monomer (i) contained in the glass ionomer cement (Y) include the monomer contained in the self-adhesive dental composite resin (X) (monomer having an acidic group (a) and monomers having no acidic group (b)), which may be used singly or in combination of two or more.

<Photoinitiator (j)>
In another preferred embodiment, the glass ionomer cement (Y) further contains a monomer (i ), and a photoinitiator (j). Specific examples of the photopolymerization initiator (j) include those similar to the photopolymerization initiator (c) contained in the self-adhesive dental composite resin (X). or two or more of them may be used in combination.

<Structure of Dental Filling Kit of the Present Invention>
The dental filling kit of the present invention comprises a self-adhesive dental composite resin (X) and a glass ionomer cement (Y), which are normally packed in separate containers. The self-adhesive dental composite resin (X) may be of a one-pack type or a two-pack type, but a one-pack type is preferred from the viewpoint of operability and curing time. The glass ionomer cement (Y) includes a two-part type consisting of two materials, a powder material and a liquid material, and a two-part type consisting of two kinds of pastes. preferable.

The dental filling kit of the present invention may be further combined with an etching material (C), a dental primer (D), a dental bonding material (E), and the like. The etchant (C) is preferably applied only to the enamel from the viewpoint of cavity sealing properties. From the viewpoints of adhesive strength to dentin and cavity sealing properties, it is preferable to combine the dental primer (D) and the dental bonding material (E), more preferably to combine the dental bonding material (E). The dental primer (D) and the dental bonding material (E) may or may not be polymerized alone, but from the viewpoint of cavity sealing properties, they are preferably polymerized by light or chemical polymerization. Each of the etching material (C), the dental primer (D), and the dental bonding material (E) may be used alone or in combination of two or more. From the viewpoint of cavity sealing properties, the procedure of applying the dental primer (D) after the use of the etching material (C) and then applying the dental bonding material (E) is preferred. Also, for example, two types of bonding materials may be used, and after applying one dental bonding material, another dental bonding material may be applied.

A conditioner may also be used in the dental filling kit of the present invention. Conditioners may be known conditioners and may be applied to the dentin prior to application of the glass ionomer cement (Y). From the viewpoint of operability, it is preferable not to use a conditioner.

<Specific application methods and procedures>

• Application of self-adhesive dental composite resin (X) After forming the cavity on the tooth substance, apply the self-adhesive dental composite resin (X). The self-adhesive dental composite resin (X) may be filled from the bottom of the cavity to the middle of the cavity, as shown in FIG. The top of the filled self-adhesive dental composite resin 3 is filled with glass ionomer cement 4 . It may also be filled to seal the entire cavity, as shown in FIG. The top of the self-adhesive dental composite resin 3 used for sealing is filled with glass ionomer cement 4 . In any form, it is preferable that the area of the self-adhesive dental composite resin 3 in contact with the dentin 1 is larger than that of the glass ionomer cement 4 . In the case of the self-adhesive dental composite resin (X) containing the photopolymerization initiator (c), it is cured by irradiation with a dental light irradiation device. In the case of self-adhesive dental composite resin (X) containing a chemical polymerization initiator, it is allowed to stand until curing is completed. After that, depending on the case, surface morphology correction and polishing are performed.

When combining an etching material (C), a dental primer (D), a dental bonding material (E), etc., they are used before applying the self-adhesive dental composite resin (X).

• Application of glass ionomer cement (Y) Glass ionomer cement (Y) is applied to the surface to which the self-adhesive dental composite resin (X) has been applied, and in some cases to the dentin. Since it is a two-part formulation, it is applied after being mixed and kneaded. After application, in the case of the glass ionomer cement (Y) containing the photopolymerization initiator (j), it is cured by light irradiation with a dental light irradiation device. When the photopolymerization initiator (j) is not included, the composition is allowed to stand until curing is completed. After that, depending on the case, surface morphology correction and polishing are performed.

In the present invention, a self-adhesive dental composite resin (X) is used to seal the whole or a part of the cavity by applying it directly to the tooth substance after forming the cavity, and the self-adhesive dental composite resin ( By further coating the surface to which X) is applied with a glass ionomer cement (Y), it is possible to obtain ion releasing properties while having excellent cavity sealing properties. Therefore, another embodiment of the present invention is that the self-adhesive dental composite resin (X) is for direct sealing of all or part of the cavity, and the glass ionomer cement (Y) is the self-adhesive dental composite resin (X). ) is for covering the surface to which ) is applied.

Yet another embodiment of the present invention comprises the steps of applying a self-adhesive dental composite resin (X) to a predetermined area of the tooth; applying a glass ionomer cement (Y) to the region, wherein the self-adhesive dental composite resin (X) comprises a monomer having an acidic group (a), a monomer having no acidic group (b), and a photopolymerization initiator (c), and the glass ionomer cement (Y) comprises a fluoroaluminosilicate glass powder (f), a polycarboxylic acid-based polymer (g), and water (h). is mentioned. Each step is as described in the specific application method and procedure above.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. In addition, the part in an example is a mass part unless otherwise specified.

Next, the components of the dental filling kits of Examples and Comparative Examples are described below with abbreviations.

・Self-adhesive dental composite resin (X)
[Monomer (a) having an acidic group]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate P-2M: bis (2-methacryloyloxyethyl) hydrogen phosphate

[Monomer (b) having no acidic group]
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane Bis-MEPP: bismethacrylate isopropylidenebis[(4,1-phenylene)oxyethylene]
UDMA: di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate D-2.6E: 2,2-bis (4-methacryloyloxy polyethoxyphenyl) propane (average number of added moles of ethoxy groups is 2.6)
3G: triethylene glycol dimethacrylate DD: 1,10-decanediol dimethacrylate MAEA: N-methacryloyloxyethylacrylamide DEAA: N,N-diethylacrylamide HEMA: 2-hydroxyethyl (meth)acrylate

[Photoinitiator (c)]
- Water-soluble photopolymerization initiator (c-1)
Li-TPO: phenyl (2,4,6-trimethylbenzoyl)phosphinic acid lithium salt/water-insoluble photopolymerization initiator (c-2)
CQ: camphorquinone BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Filler (d)]
Filler 1: Nippon Aerosil Co., Ltd., ultrafine silica "Aerosil (registered trademark) R 972", average particle size: 16 nm
Filler 2: Silane-treated silica OX50 (manufactured by Nippon Aerosil Co., Ltd., ultrafine silica "Aerosil (registered trademark) OX50", average particle size: 0.04 μm) 100 g, γ-methacryloyloxypropyltrimethoxysilane 7 g, and 0.3 200 mL of a mass % acetic acid aqueous solution was placed in a three-necked flask and stirred for 2 hours at room temperature. After water was removed by freeze-drying, heat treatment was performed at 80° C. for 5 hours to obtain filler 2.
Filler 3: Silane-treated silica powder Silica 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.
Filler 4: 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.
Filler 5: Silane-treated barium glass powder GM27884 NF180 grade (SCHOTT barium glass, average particle size: 0.18 μm) 100 g, γ-methacryloyloxypropyltrimethoxysilane 13 g, and 0.3% by mass acetic acid aqueous solution 200 mL were placed in a three-necked flask. and stirred for 2 hours at room temperature. After water was removed by freeze-drying, heat treatment was performed at 80° C. for 5 hours to obtain filler 5.
Filler 6: Silane-treated barium glass powder 8235 UF0.7 grade (SCHOTT barium glass, average particle size: 0.7 μm) 100 g, γ-methacryloyloxypropyltrimethoxysilane 6 g, and 0.3 mass% acetic acid aqueous solution 200 mL It was placed in a three-necked flask and stirred at room temperature for 2 hours. After water was removed by freeze-drying, heat treatment was performed at 80° C. for 5 hours to obtain filler 6.
Filler 7: Silane-treated spherical silica-titania composite oxide powder Three mouths of 100 g of spherical silica-titania composite oxide (average particle size: 0.3 μm), 10 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3% by mass aqueous acetic acid solution. It was placed in a flask and stirred for 2 hours at room temperature. After water was removed by freeze-drying, heat treatment was performed at 80° C. for 5 hours to obtain filler 7 .
Silica powder: Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.)
Strontium glass powder: SiO ₂ (55% by mass), Al ₂ O ₃ (10% by mass), SrO (20% by mass) and B ₂ O ₃ (15% by mass) were sufficiently mixed to obtain a raw material composition. Next, using a high-temperature electric furnace, the raw material composition was held at 1200° C. for 5 hours, melted, and then cooled to obtain strontium glass. Next, the strontium glass was pulverized for 10 hours using a ball mill and passed through a 200-mesh (ASTM) sieve to obtain strontium glass powder.
Barium glass powder: SiO ₂ (55% by mass), Al ₂ O ₃ (10% by mass), BaO (30% by mass) and B ₂ O ₃ (10% by mass) were sufficiently mixed to obtain a raw material composition. Next, using a high-temperature electric furnace, the raw material composition was held at 1200° C. for 5 hours, melted, and then cooled to obtain barium glass. Next, after pulverizing the barium glass for 10 hours using a ball mill, it was passed through a 200-mesh (ASTM) sieve to obtain barium glass powder.

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

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

・Glass ionomer cement (Y)
[Fluoroaluminosilicate glass powder (f)]
Aluminum oxide (21% by mass), silicic anhydride (44% by mass), calcium fluoride (12% by mass), calcium phosphate (14% by mass), and strontium carbonate (9% by mass) are sufficiently mixed to obtain a raw material composition. rice field. Next, using a high-temperature electric furnace, the raw material composition was held at 1200° C. for 5 hours, melted, and then cooled to obtain a fluoroaluminosilicate glass. Next, the fluoroaluminosilicate glass was pulverized using a ball mill for 10 hours and passed through a 200-mesh (ASTM) sieve to obtain a fluoroaluminosilicate glass powder.

[Polyacrylic acid polymer (g)]
Polyacrylic acid powder (weight average molecular weight: 25,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in water to obtain a 50% by mass polyacrylic acid aqueous solution.

[Examples 1 to 20 and Comparative Examples 1 to 5]
[Preparation of self-adhesive dental composite resin (X)]
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 self-adhesive dental composite resin, and the properties were examined according to the methods of Test Examples 1 to 3 below. . The results are shown in Tables 1-4.

[Kneading of glass ionomer cement (Y)]
A fluoroaluminosilicate glass powder and an aqueous polyacrylic acid solution were kneaded at a powder-to-liquid ratio (powder/liquid) of 1.8 to obtain a kneaded product of glass ionomer cement.

Test Example 1 Adhesion strength when self-adhesive dental composite resin and glass ionomer cement are laminated [Shear adhesion test to dentin]
The lip surfaces of bovine mandibular anterior teeth were polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain samples in which the flat surface of dentin was exposed. A tape was attached to the bottom surface of a mold having 15 holes (15-hole mold, manufactured by Ultradent, φ35 mm×height 25 mm), and a sample tooth was fixed thereon. Gypsum was filled in the mold and allowed to stand for about 30 minutes to harden the gypsum. Remove the sample from the mold, polish it with #600 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to a size (φ2.38 mm or more) that can secure the adherend surface, and ultrasonically for 5 minutes.

A separately prepared CR filling mold (Bonding Mold Insert, manufactured by Ultradent) with a diameter of 2.38 mm was attached to a special tool (Bonding Clamp, manufactured by Ultradent). Next, the CR filling mold attached to the dedicated tool was lowered so that the CR filling mold was in close contact with the adherend surface of the sample, and the sample was fixed. Next, the dental composite resin prepared in each example and comparative example was thinly filled into the hole of the CR filling mold to a thickness of 1 mm or less. After being left for 10 seconds, the self-adhesive dental composite resin was cured by light irradiation for 10 seconds with a dental LED light irradiator (manufactured by Ultradent, trade name "VALO"). Thereafter, the glass ionomer cement was filled in the mold (up to about 2/3 of the mold, total thickness of about 2 mm) and stored for 10 minutes in an environment of 37°C and 95% RH to harden the glass ionomer cement. The sample was removed from the mold and used as an adhesion test sample. Next, the adhesion test sample was immersed in distilled water in the sample container, left in a constant temperature chamber set at 37° C. for 24 hours, and then taken out to measure the adhesion strength. Adhesion strength (shear adhesion strength) is measured by attaching the adhesion test test sample to a special holder (Test Base Clamp, manufactured by Ultradent), using a dedicated jig (Crosshead Assembly, manufactured by Ultradent) and a universal testing machine ( (manufactured by Shimadzu Corporation), the crosshead speed was set to 1 mm/min, and the average values are shown in the table (n=10).

Test Example 2 Cavity Sealability The surface of a bovine tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain samples in which the flat surface of the enamel was exposed. Using Manny Diabar SF-21 (manufactured by Manny Co., Ltd.), a cylindrical cavity with a diameter of 4 mm and a depth of 2 mm was formed with an air turbine while pouring water. After the formation, the inside of the cavity was washed with running water and then dried with an air blow.
Pattern 1: Fill the self-adhesive dental composite resin to a depth of less than 1 mm so as to seal the inside of the cavity, leave it for 10 seconds, and then use a dental LED light irradiator (manufactured by Ultradent, trade name "VALO"). ) was irradiated for 10 seconds. After that, it was filled with glass ionomer cement and stored in an environment of 37° C. and 95% RH for 10 minutes to harden the glass ionomer cement and obtain a test sample.
Pattern 2: The glass ionomer cement was filled to a depth of less than 1 mm so as to seal the inside of the cavity, and stored in an environment of 37°C and 95% RH for 10 minutes to harden the glass ionomer cement. Then, a self-adhesive dental composite resin was filled and irradiated with a dental LED light irradiator (manufactured by Ultradent, trade name "VALO") for 10 seconds to obtain a test sample.

For both patterns 1 and 2, the samples were observed with an optical coherence tomography (OCT, IVS-2000, Santec Co., Ltd.) to evaluate the suitability of the cavity (n=3). A score of 0 is given for a sample with no peeling of the cavity, a score of 1 is given for a sample with at least one peeling on the side of the cavity, a score of 2 is given for a sample with at least one peeling at the bottom of the cavity, and a score of 2 is given for a sample with at least one peeling on the side of the cavity. A score of 3 was given to samples in which peeling of the fovea bottom was observed.

Test Example 3 Fluoride ion release assuming a real cavity A mold with a diameter of 20 mm and a thickness of 2 mm was filled with a self-adhesive dental composite resin of about 1 mm, and a dental LED light irradiation device (manufactured by Ultradent, product (named "VALO") was irradiated from above for 10 seconds, and a total of 9 points were irradiated so that the entire filling was exposed to light. Then, the rest of the mold was filled with the glass ionomer cement and stored for 10 minutes in an environment of 37° C. and 95% RH to harden the glass ionomer cement. A cavity was simulated by covering the sides and the bottom of the cured product with nail polish, except for the upper surface. In that state, it was immersed in 10 ml of phosphate buffer (pH 7, 37° C.). Fluoride ions eluted in the phosphate buffer solution were quantified with a fluoride ion electrode (LAQUA PH/ION METER F-73, manufactured by Horiba, Ltd.) after 28 days of immersion, and the average fluoride ion release amount per 1 g of the cured product was determined. (μg/g) was calculated (n=3). In the comparative example, after hardening the glass ionomer cement, a self-adhesive dental composite resin was filled, and the side surfaces and the bottom surface of the hardened material other than the upper surface were covered with nail polish to simulate a cavity.

（表中、窩底部側の材料が「実施例１」であるとは、窩底部側に実施例１の自己接着性歯科用コンポジットレジンを適用したことを意味する。）

(In the table, the fact that the material of the cavity bottom side is "Example 1" means that the self-adhesive dental composite resin of Example 1 was applied to the cavity bottom side.)

From the results in Tables 1 and 2, the dental filling kits of Examples 1 to 19 had an adhesion strength to dentin of 7 MPa or more and a cavity sealing score of 1 or less. On the other hand, as shown in Table 3, Comparative Examples 1 to 4 had a score of 1 in pattern 2 and exhibited good cavity sealing properties, but all had a score of 2 in pattern 1. Furthermore, in Comparative Examples 1 to 4, the adhesion strength to dentin was as low as 5 MPa or less. Since Comparative Examples 1 and 3 correspond to Examples 1 and 4 of Patent Document 5, respectively, advantageous effects of the present invention over the prior art were confirmed. As shown in Table 4, in Example 20, the method of filling the cavity bottom with self-adhesive dental composite resin and filling the cavity surface with glass ionomer cement yielded a high fluorine release amount. In contrast, in Comparative Example 5, almost no release occurred.

The dental filling kit of the present invention can be suitably used for filling treatment in dental treatment. The dental filling kit of the present invention can be used particularly preferably for filling a cavity of 2 mm or more.

1: dentin 2: enamel 3: self-adhesive dental composite resin 4: glass ionomer cement

Claims (10)

a self-adhesive dental composite resin (X) comprising a monomer (a) having an acidic group, a monomer (b) having no acidic group, and a photopolymerization initiator (c);
A fluoroaluminosilicate glass powder (f), a polycarboxylic acid polymer (g), and a glass ionomer cement (Y) containing water (h),
A dental filling kit, wherein the content of the monomer (a) having an acidic group is 1 to 30 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). The self-adhesive dental composite resin (X) further contains a filler (d), and the content of the filler (d) is 50 to 90 parts per 100 parts by mass of the self-adhesive dental composite resin (X). A dental filling kit according to claim 1, which is a mass. The dental according to claim 2, wherein the filler (d) includes a filler (d-ii) having an average particle size of 0.1 µm or more and 1 µm or less and/or a filler (d-iii) having an average particle size of more than 1 µm and 10 µm or less. filling kit. The filler (d-ii) and/or the filler (d-iii) includes an inorganic filler containing a silicon atom and/or an inorganic filler composed of an oxide of a silicon atom, and the inorganic filler has hydroxyl groups on the surface. The dental filling kit according to claim 3, wherein the hydroxyl groups are surface-treated with a surface-treating agent. The filler (d) is a combination (I) of a filler (d-i) having an average particle size of 1 nm or more and less than 0.1 μm and a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less, and the average particle A combination (II) of a filler (d-i) having a diameter of 1 nm or more and less than 0.1 μm and a filler (d-iii) having an average particle diameter of more than 1 μm and 10 μm or less (d-iii), a filler having an average particle diameter of 1 nm or more and less than 0.1 μm (d -i), a combination (III) of a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less and a filler (d-iii) having an average particle size of more than 1 μm and 10 μm or less, and an average particle size of 0. The dental filling kit according to any one of claims 2 to 4, comprising at least one combination selected from the group consisting of combinations (IV) of fillers (d-ii) having a size of 1 μm or more and 1 μm or less. A dental filling kit according to any one of claims 1 to 5, wherein said glass ionomer cement (Y) further comprises a monomer (i) and a photopolymerization initiator (j). The dental filling kit according to any one of claims 1 to 6, wherein the self-adhesive dental composite resin (X) is a one-pack type. The dental filling according to any one of claims 1 to 7, wherein the content of the fluoroaluminosilicate glass powder (f) is 25 to 85 parts by mass in 100 parts by mass of the total amount of the glass ionomer cement (Y). Kit for. The self-adhesive dental composite resin (X) is for direct sealing of the whole or part of the cavity, and the glass ionomer cement (Y) is for covering the surface to which the self-adhesive dental composite resin (X) is applied. The dental filling kit according to any one of claims 1 to 8, wherein Applying a self-adhesive dental composite resin (X) to a predetermined area of the tooth and applying a glass ionomer cement (Y) to the predetermined area to which the self-adhesive dental composite resin (X) was applied. including the process,
The self-adhesive dental composite resin (X) comprises a monomer having an acidic group (a), a monomer having no acidic group (b), and a photopolymerization initiator (c),
A method for restoring teeth, wherein the glass ionomer cement (Y) contains a fluoroaluminosilicate glass powder (f), a polycarboxylic acid-based polymer (g), and water (h).

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