JP7237543B2 - dental composite resin - Google Patents

Description

The present invention relates to dental composite resins.

BACKGROUND ART Conventionally, dental adhesives and dental composite resins have been commonly used for restoration of dental caries and accompanying defects. Restorative treatments are performed according to the following procedure. First, after a carious portion is shaved to form a cavity, a dental adhesive is applied to the cavity, and then visible light is applied to the adhesive-applied site to cure the adhesive. Next, the hardened adhesive layer is filled with a dental composite resin, and finally the filled dental composite resin is irradiated with visible light to harden it.

In the restoration method described above, two materials, a dental adhesive and a dental composite resin, are used. Recently, a self-adhesive dental composite resin has been developed in which the dental composite resin itself has adhesive properties. It is beginning to be put to practical use as a material that can omit the use of dental adhesives and reduce the number of operating steps in restorative treatment.

The self-adhesive dental composite resin contains, for example, a crosslinkable monomer for imparting mechanical strength, a filler, and a polymerization initiator for improving hardening properties, in addition to the conventional dental composite resin components. In addition, it further contains a monomer having an acidic group, which has been conventionally used in dental adhesives, in order to impart adhesiveness to tooth substance (see, for example, Patent Documents 1 and 2).

In relation to the self-adhesive dental composite resin, US Pat.
a) a radically polymerizable component having an acidic moiety as component (A);
b) as component (B), a radically polymerizable component that does not have an acidic moiety;
c) an oxidizing agent comprising a persulfate as component (C);
d) a transition metal component as component (D);
e) as component (E) a photoinitiator system;
f) optionally, as component (F), a non-acid-reactive filler;
g) optionally as component (G), an additive,
Compositions are described that do not contain basic fillers.

Patent Document 4 describes a dental adhesive material kit composed of a dental water-based adhesive composition (A) and a dental hardening composition (B). The composition (A) comprises an acidic group-containing (meth)acrylic polymerizable monomer (a), a vanadium compound (b), water (c), an amino group-containing (meth)acrylic polymerizable The dental curable composition (B) contains a monomer (d) and a polymerization inhibitor (i), and contains a (meth)acrylic polymerizable monomer (e) containing no acidic group, a hydroper A two-component dental adhesive material kit containing an oxide (f), a photoinitiator (g) and a filler (h) and containing no thiourea compound is described in Patent Document 4. There is no description of a self-adhesive dental composite resin, nor is there a description of mixing a dental water-based adhesive composition (A) and a dental curable composition (B).

JP 2008-260752 A EP-A-2153811 Japanese Patent Application Publication No. 2015-507610 WO2017/104128

The conventional self-adhesive dental composite resins described in Patent Documents 1 and 2, etc. have room for further improvement in terms of adhesiveness. In addition, although the adhesiveness of the one-component self-adhesive composition described in Patent Document 3 is somewhat improved, as a result of investigations by the present inventors, the photopolymerization initiator contained therein is easily decomposed. It has been found that the storage stability is poor and the cured product tends to discolor after curing.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a dental composite resin which is excellent in storage stability and adhesiveness and which can suppress discoloration of the cured product.

The present inventors have made intensive studies to achieve the above object, and as a result, have found that conventional self-adhesive dental products containing a monomer having an acidic group, a monomer having no acidic group, a photopolymerization initiator and a filler By adding a vanadium compound and not containing a persulfate to the composite resin for , it surprisingly has excellent storage stability and adhesiveness, and suppresses discoloration of the cured product. The present inventors have found that the composite resin for dental use can be made into a composite resin that can be produced, and have completed the present invention through further studies based on this finding.

That is, the present invention relates to the following.
[1] a monomer having an acidic group (a), a monomer having no acidic group (b), a vanadium compound (c), a photopolymerization initiator (d) and a filler (e), and a persulfate A dental composite resin substantially free of
[2] The dental composite resin according to [1], wherein the vanadium compound (c) is an IV-valent and/or V-valent vanadium compound.
[3] The vanadium compound (c) is divanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis(1-phenyl-1,3- butanedionate)vanadium (IV), bis(maltrate)oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V) and ammonium metavanadate (V). , a dental composite resin according to [1].
[4] The content of the vanadium compound (c) is 0.001 to 10 parts by mass with respect to 100 parts by mass of all the monomers, [1] to [3]. dental composite resin.
[5] The monomer (a) having an acidic group is a (meth)acrylic monomer having a phosphoric acid group and/or a (meth)acrylic monomer having a carboxylic acid group, [1 ] The dental composite resin according to any one of [4].
[6] The dental composite according to any one of [1] to [4], wherein the monomer (a) having an acidic group is a (meth)acrylic monomer having a phosphoric acid group. resin.
[7] Any one of [1] to [6], wherein the content of the monomer (a) having an acidic group is 1 to 40 parts by mass with respect to 100 parts by mass of the total monomers. A dental composite resin according to .
[8] The dental composite according to any one of [1] to [7], wherein the content of the filler (e) is 100 to 900 parts by mass with respect to 100 parts by mass of the total monomers. resin.
[9] The dental composite resin according to any one of [1] to [8], which is a single material type.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a dental composite resin which is excellent in storage stability and adhesiveness and capable of suppressing discoloration of the cured product.

[Dental Composite Resin]
The dental composite resin of the present invention comprises a monomer having an acidic group (a), a monomer having no acidic group (b), a vanadium compound (c), a photopolymerization initiator (d) and a filler (e). and substantially free of persulfates. With this structure, the dental composite resin is excellent in storage stability and adhesiveness, and can suppress discoloration of the cured product.

- A monomer having an acidic group (a)
The monomer (a) having an acidic group not only promotes demineralization of tooth substance and improves adhesion to tooth substance, but also promotes chemical polymerization at the adhesion interface.

As the monomer (a) having an acidic group, for example, a polymerizable monomer having at least one acidic group and at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, a styrene group, etc. and the like, and (meth)acrylic monomers having an acidic group, such as (meth)acrylic esters having an acidic group and (meth)acrylamide having an acidic group, are preferred, and (meth)acrylic monomers having an acidic group are preferred. Acid esters are more preferred, and methacrylic acid esters having an acidic group are even more preferred. In this specification, the term "(meth)acryl" is used in the sense of including both methacryl and acryl.
Examples of the acidic group include a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, a sulfonic acid group, and the like. You may have only 1 type in an acidic group, and may have 2 or more types.
The monomer (a) having an acidic group may be used alone or in combination of two or more. Specific examples of (meth)acrylic monomers having various acidic groups, which can be preferably used as the monomer (a) having an acidic group, are shown below.

(Meth)acrylic monomers having a phosphoric acid group include, for example, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyl oxybutyl dihydrogen phosphate, 5-(meth) acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) ) acryloyloxyoctyl dihydrogen phosphate, 9-(meth) acryloyloxy nonyl dihydrogen phosphate, 10-(meth) acryloyloxydecyl dihydrogen phosphate, 11-(meth) acryloyloxy undecyl dihydrogen phosphate, 12 -(meth) acryloyl oxide decyl dihydrogen phosphate, 16-(meth) acryloyloxy hexadecyl dihydrogen phosphate, 20-(meth) acryloyloxy eicosyl dihydrogen phosphate, 2-(meth) acryloyloxyethyl phenyl hydro gen phosphate, 2-(meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth) acryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate, 2-(meth) acryloyloxypropyl (4-methoxy Monofunctional (meth) acrylic monomers having a phosphoric acid group such as phenyl) hydrogen phosphate, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts; [2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth ) acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di(meth)acryloyloxypropyl Dihydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl Polyfunctional (meth)acrylic monomers having a phosphoric acid group such as [chill] hydrogen phosphate, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts, etc. mentioned.

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

Examples of (meth)acrylic monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth) ) acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate Phosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyl oxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyl oxide decyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogen Thiophosphates, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

Examples of (meth)acrylic monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth) ) acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecyl Phosphonoacetates, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

The (meth)acrylic monomer having a carboxylic acid group includes a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.

Polymerizable monomers having one carboxyl group in the molecule include, for example, (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth)acryloyloxyethyl Hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogenmalate, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine 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, and their acid anhydrides and acid halides (acid chlorides, etc.), Examples include alkali metal salts and ammonium salts.

Polymerizable monomers having multiple carboxyl groups in the molecule include, for example, 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 13- (Meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate , 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3′-(meth)acryloyloxy-2′-(3,4-dicarboxybenzoyloxy)propylsuccinate, 6- (Meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 6-(meth)acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid, 4-(meth)acryloyloxyethylcarbonylpropionoyl-1 ,8-naphthalic acid, 4-(meth)acryloyloxyethylnaphthalene-1,8-tricarboxylic acid, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts, etc. .

Examples of (meth)acrylic monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, and their acid anhydrides and acid halides. (acid chloride, etc.), alkali metal salts, ammonium salts, and the like.

Among the monomers (a) having an acidic group, a (meth)acrylic monomer having a phosphoric acid group is preferred because it improves adhesiveness when used as a self-adhesive dental composite resin. and/or a (meth)acrylic monomer having a carboxylic acid group is preferred, such as 2-methacryloyloxyethyl dihydrogenphosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, bis(2-methacryloyloxyethyl) Acid anhydrides of hydrogen phosphate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, and 4-(meth)acryloyloxyethyl trimellitate are more preferable. , 10-methacryloyloxydecyl dihydrogen phosphate is more preferred. As the monomer (a) having an acidic group, a (meth)acrylic monomer having a phosphoric acid group is particularly preferred.

The content of the monomer (a) having an acidic group is not particularly limited. It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of all monomers contained in the composite resin. It is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

- A monomer (b) having no acidic group
As the monomer (b) having no acidic group, for example, a polymerizable monomer having no acidic group and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, a styrene group, etc. and the like, and a (meth)acrylic monomer having no acidic group, such as (meth)acrylic acid ester having no acidic group or (meth)acrylamide having no acidic group, is preferable, and has no acidic group ( A meth)acrylic acid ester is more preferred, and a methacrylic acid ester having no acidic group is even more preferred. The monomer (b) having no acidic group may be used alone or in combination of two or more.

Examples of the monomer (b) having no acidic group include (i) an aromatic bifunctional (meth)acrylic acid ester, (ii) an aliphatic bifunctional (meth) Acrylic acid esters, (iii) trifunctional or higher (meth)acrylic acid esters, and the like.

(i) Aromatic bifunctional (meth)acrylic acid ester Examples of the aromatic bifunctional (meth)acrylic acid ester include 2,2-bis((meth)acryloyloxyphenyl)propane , 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (common name: Bis -GMA), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (e.g., the average number of added moles of ethoxy groups is 2.6), 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)acryloyloxypropoxyphenyl) ) propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 2-(4-(meth)acryloyl oxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl) Propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, among others, 2,2-bis[4-( 3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (common name: Bis-GMA), 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (with an average number of added moles of ethoxy groups of 2.6 Common name: D-2.6E) is preferred.

(ii) Aliphatic Bifunctional (Meth)Acrylic Acid Esters Examples of aliphatic bifunctional (meth)acrylic acid esters include glycerol di(meth)acrylate and ethylene glycol di(meth)acrylate. , diethylene glycol di(meth)acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (common name: TEGDMA), propylene glycol di(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, 2, 2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) diacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (common name: UDMA), 1,2-bis(3 - (meth) acryloyloxy-2-hydroxypropoxy) ethane and the like, among them, glycerol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (common name: TEGDMA), neopentyl glycol di (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (common name) : UDMA), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane are preferred.

(iii) Trifunctional or higher (meth)acrylic acid ester Trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylol Methane 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-di(meth)acryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxa heptane and the like, and among these, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

The above aromatic bifunctional (meth)acrylic acid ester, aliphatic bifunctional (meth)acrylic acid ester and trifunctional or higher (meth)acrylic acid ester are used alone. You may use and you may use 2 or more types together. Among these, aromatic bifunctional (meth)acrylic acid esters and aliphatic bifunctional ( meth)acrylic acid esters are preferred, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (common name: Bis-GMA), 2,2-bis(4-methacryloyloxy polyethoxy Phenyl)propane (having an average number of added moles of ethoxy groups of 2.6, commonly known as D-2.6E), triethylene glycol dimethacrylate (commonly known as TEGDMA), 2,2,4-trimethylhexamethylene bis(2 -Carbamoyloxyethyl) dimethacrylate (common name: UDMA) is more preferable, triethylene glycol dimethacrylate (common name: TEGDMA), 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (common name: UDMA) ) is more preferred.

The aromatic bifunctional (meth)acrylic acid ester, the aliphatic bifunctional (meth)acrylic acid ester, and the trifunctional or higher (meth)acrylic acid ester in the dental composite resin of the present invention. The total content of the acid ester is not particularly limited, but the dental acid ester of the present invention improves the curability, permeability and adhesiveness to the tooth substance, and also improves the mechanical strength of the resulting cured product. It is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and 60 parts by mass with respect to 100 parts by mass of all the monomers contained in the composite resin for use. It is particularly preferably at least 95 parts by mass, more preferably at most 90 parts by mass, even more preferably at most 85 parts by mass, and at most 80 parts by mass. is particularly preferred, and 75 parts by mass or less is most preferred.

(iv) Polyfunctional (meth)acrylamide having two or more polymerizable groups Another example of the monomer (b) having no acidic group is (iv) having two or more polymerizable groups Polyfunctional (meth)acrylamides can be mentioned. In the polyfunctional (meth)acrylamide, the two or more polymerizable groups it has may all be (meth)acrylamide groups, or some of them may be (meth)acryloyloxy groups, Polymerizable groups other than (meth)acrylamide groups such as vinyl groups and styrene groups may also be used. Also, the polyfunctional (meth)acrylamide preferably has at least one amide proton. The polyfunctional (meth)acrylamide has at least one (meth)acrylamide group (preferably amide proton), so it has high hydrophilicity, easily penetrates into the collagen layer of dentin, and is intramolecularly Since it has a plurality of polymerizable groups, it exhibits extremely high curability together with other components of the dental composite resin of the present invention, so that higher adhesion to dentin can be obtained. Become.

Examples of polyfunctional (meth)acrylamides having two or more polymerizable groups include compounds (iv-1) represented by the following general formula (vi-1), and general formula (vi-2) below. and compound (iv-2) represented by the following general formula (vi-3), and the like.

In general formula (vi-1) above, R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted alkylene group having 1 to 8 carbon atoms (linear or branched). good) and p is an integer from 1 to 6. However, multiple R ¹ and R ² may be the same or different from each other.

In general formula (vi-2) above, R ³ is a hydrogen atom or a methyl group, and R ⁴ is an optionally substituted alkylene group having 1 to 8 carbon atoms (linear or branched). good) and q is 2 or 3. However, multiple R ³ and R ⁴ may be the same or different from each other.

In the above general formula (vi-3), R ⁵ is an optionally substituted aliphatic group having 1 to 8 carbon atoms (which may be linear, branched or cyclic) or a substituted is an aromatic group that may be provided that the aliphatic groups are -O-, -S-, -CO-, -CO-O-*, -O-CO-*, -NR ⁶ -, -CO-NR ⁶ -*, -NR ⁶ may be interrupted by at least one linking group selected from the group consisting of -CO-*, -O-CONR ⁶ -*, -NR ⁶ CO-O-* and -NR ⁶ -CO-NR ⁶ - . Here, * indicates the oxygen atom side, which is the side of the nitrogen atom to which R ⁵ is directly bonded and the side of the oxygen atom to which R ⁵ is directly bonded. R ⁶ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (which may be linear, branched or cyclic), and multiple R ⁶ They may be the same or different.

In general formulas (vi-1) and (vi-2) above, R ¹ and R ³ are preferably hydrogen atoms from the viewpoint of adhesiveness to tooth substance and curability.

In the above general formulas (vi-1) and (vi-2), R ² and R ⁴ are each an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 2 to 8 carbon atoms, An alkylene group having 2 to 4 carbon atoms is more preferable, and an alkylene group having 2 or 3 carbon atoms is even more preferable. One or more of the hydrogen atoms in the alkylene group may be substituted with a substituent, but it is preferably not substituted with a substituent.

In general formulas (vi-1) and (vi-2) above, examples of R ² and R ⁴ include methylene group, methylmethylene group, ethylene group, 1-methylethylene group, trimethylene group and 1-ethylethylene group. , 1,2-dimethylethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, 1-propylethylene group, 2-propylethylene group, 1-ethyl -1-methylethylene group, 1-ethyl-2-methylethylene group, 1,1,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, pentamethylene group, 1-butylethylene group, 1-methyl-1-propylethylene group, 1-methyl-2-propylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, hexamethylene group and the like.

In the above general formula (vi-1), p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, more preferably 1 or 2, and 2 Especially preferred. Further, q is preferably 3 in the above general formula (vi-2).

In general formula (vi-3) above, the aliphatic group having 1 to 8 carbon atoms which may have a substituent represented by R ⁵ includes a saturated aliphatic group (alkylene group, cycloalkylene group (1 , 4-cyclohexylene group, etc.) and unsaturated aliphatic groups (alkenylene group, alkynylene group, etc.). A saturated aliphatic group is preferred, and an alkylene group is more preferred. Specific examples of the alkylene group are the same as those described above for R ² and R ⁴ in formulas (vi-1) and (vi-2). From the viewpoint of adhesion and curability to tooth substance, R ⁵ is preferably an optionally substituted aliphatic group having 1 to 4 carbon atoms, and a carbon atom optionally having a substituent. More preferably, it is an aliphatic group having 2 to 4 numbers.

In the above general formula (vi-3), the optionally substituted aliphatic group represented by R ⁵ having 1 to 8 carbon atoms may be interrupted by at least one of the above-described bonding groups. good. That is, at least one bonding group described above may be inserted into the aliphatic group. When the aliphatic group is interrupted by the linking group, the number of linking groups is not particularly limited, and can be about 1 to 10, preferably 1 to 3, more preferably 1. or two. In addition, it is preferable that the aliphatic group is not interrupted by the continuous linking group. That is, it is preferred that the bonding groups are not adjacent to each other.

In the general formula (vi-3), the aliphatic group having 1 to 8 carbon atoms which may have a substituent represented by R ⁶ constituting a part of the bonding group includes a saturated aliphatic group (alkyl group, cycloalkylene group (cyclohexyl group, etc.), etc.) and unsaturated aliphatic group (alkenyl group, alkynyl group, etc.). From the viewpoint, it is preferably a saturated aliphatic group, and more preferably an alkyl group. Examples of the alkyl group 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, n- Examples include hexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group and the like. R ⁶ is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 3 carbon atoms. is more preferable.

The binding groups include -O-, -S-, -CO-, -CO-O-*, -O-CO-*, -NH-, -CO-NH-*, -NH-CO-*, -O-CONH-*, -NHCO-O-* and -NH-CO-NH- is preferably at least one selected from the group consisting of -O-, -S-, -CO-, -NH-, - At least one selected from the group consisting of CO-NH-* and -NH-CO-* is more preferred.

In general formula (vi-3) above, examples of the optionally substituted aromatic group represented by R ⁵ include an aryl group and an aromatic heterocyclic group. Preferred is a phenyl group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated, for example, furan group, thiophene group, pyrrole group, oxazole group, isoxazole group, thiazole group, isothiazole group, imidazole group, pyrazole group, furazane group, triazole group, pyran group, pyridine group, pyridazine group, pyrimidine group, pyrazine group, 1,3,5-triazine group and the like. The aromatic heterocycle is preferably a 5- or 6-membered ring.

In the general formulas (vi-1), (vi-2) and (vi-3), examples of substituents that R ² , R ⁴ and R ⁵ may have include halogen atoms (fluorine atoms, chlorine atom, bromine atom, iodine atom), carboxy group, hydroxyl group, amino group, amino group mono- or di-substituted with alkyl group having 1 to 8 carbon atoms, acyl group, acyloxy group, amido group, carbon number 2 to 8 alkoxycarbonyl groups, alkoxy groups having 1 to 8 carbon atoms, alkylthio groups having 1 to 8 carbon atoms, etc., and halogen atoms are preferred. The number of substituents is not particularly limited, and can be about 1 to 8, preferably 1 to 3.

Specific examples of the compound (iv-1) represented by the general formula (iv-1) include those shown below.

Among these, compounds represented by formula (iv-1-1) (iv-1-1) and compounds represented by formula (iv-1-3) are considered from the viewpoint of adhesiveness and curability to tooth substance. (iv-1-3), compound (iv-1-5) represented by formula (iv-1-5), compound (iv-1-7) represented by formula (iv-1-7) Preferably, compound (iv-1-1) represented by formula (iv-1-1), more preferably compound (iv-1-5) represented by formula (iv-1-5), Compound (iv-1-5) represented by formula (iv-1-5) is more preferable from the viewpoint of high hydrophilicity related to penetration into the collagen layer.

Specific examples of the compound (iv-2) represented by the general formula (iv-2) include those shown below.

Among these, compounds represented by formula (iv-2-1) (iv-2-1) and compounds represented by formula (iv-2-3) are considered from the viewpoint of adhesiveness and curability to tooth substance. (iv-2-3), compound (iv-2-5) represented by formula (iv-2-5), compound (iv-2-7) represented by formula (iv-2-7) Preferably, compound (iv-2-1) represented by formula (iv-2-1), compound (iv-2-3) represented by formula (iv-2-3) is more preferable, and dentin Compound (iv-2-1) represented by formula (iv-2-1) is more preferable from the viewpoint of high hydrophilicity related to penetration into the collagen layer.

Specific examples of the compound (iv-3) represented by the general formula (iv-3) include those shown below.

Among these, the compound (iv-3-1) represented by the formula (iv-3-1), the compound represented by the formula (iv-3-3), from the viewpoint of adhesiveness and curability to tooth substance (iv-3-3), compound (iv-3-4) represented by formula (iv-3-4), compound (iv-3-9) represented by formula (iv-3-9), Compound (iv-3-10) represented by formula (iv-3-10) is preferable, and from the viewpoint of high hydrophilicity related to penetration into the collagen layer of dentin, formula (iv-3-1) The compound (iv-3-1) represented by the formula (iv-3-4) is more preferably the compound (iv-3-4) represented by the formula (iv-3-1) (iv-3-1) is more preferred.

Polyfunctional (meth)acrylamides having two or more polymerizable groups may be used singly or in combination of two or more. In particular, when at least one selected from the group consisting of compound (iv-1) and compound (iv-2) is used in combination with compound (iv-3), the effects of the present invention are exhibited more remarkably. preferred from

The content of the polyfunctional (meth)acrylamide having two or more polymerizable groups in the dental composite resin of the present invention is not particularly limited, but the curability and adhesiveness are improved, and the resulting curing The amount is preferably 0.5 parts by mass or more, and 2 parts by mass or more based on 100 parts by mass of all monomers contained in the dental composite resin of the present invention, because the mechanical strength of the product is improved. more preferably 4 parts by mass or more, particularly preferably 7 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less , and 20 parts by mass or less.

(v) Hydrophilic monofunctional polymerizable monomer Still another example of the monomer (b) having no acidic group is (v) a hydrophilic monofunctional polymerizable monomer. mentioned. The hydrophilic monofunctional polymerizable monomer typically has no acidic group and only one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group or a styrene group. The hydrophilic monofunctional polymerizable monomer preferably has a solubility in water (pure water) at 25° C. of 5% by mass or more, more preferably 10% by mass or more. , and the solubility thereof is more preferably 15% by mass or more. By including the hydrophilic monofunctional polymerizable monomer in the dental composite resin of the present invention, higher adhesion to dentin can be obtained.

A hydrophilic monofunctional polymerizable monomer has a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group and an amide group. Examples of hydrophilic monofunctional polymerizable monomers include hydrophilic monofunctional (meth)acrylic acid esters, hydrophilic monofunctional (meth)acrylamides, and other hydrophilic monofunctional ( Meth)acrylic monomers are preferred.

Examples of hydrophilic monofunctional (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxy -2-propyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyltrimethylammonium chloride and the like.

Hydrophilic monofunctional (meth)acrylamides include, for example, compounds represented by the following general formula (v-1), N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N -bis(hydroxyethyl)(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, 4-(meth)acryloylmorpholine, N-tri(hydroxymethyl) methyl-N-methyl(meth)acrylamide and the like.

In general formula (v-1) above, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.). However, multiple R ⁸ may be the same or different.

Among these hydrophilic monofunctional (meth)acrylic monomers, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and general A compound represented by the formula (v-1), diacetone (meth)acrylamide is preferred, 2-hydroxyethyl (meth)acrylate, more preferably a compound represented by the general formula (v-1), 2-hydroxyethyl methacrylate , N,N-diethylacrylamide is more preferred.

One hydrophilic monofunctional polymerizable monomer may be used alone, or two or more thereof may be used in combination.

The content of the hydrophilic monofunctional polymerizable monomer in the dental composite resin of the present invention is not particularly limited, but the curability and adhesiveness are improved, and the mechanical strength of the resulting cured product is is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of all monomers contained in the dental composite resin of the present invention. It is more preferably at least 7 parts by mass, particularly preferably at least 7 parts by mass, preferably at most 30 parts by mass, more preferably at most 28 parts by mass, and at most 25 parts by mass. is more preferably 20 parts by mass or less, and most preferably 12 parts by mass or less.

Examples of the monomer (b) having no acidic group include the above-described aromatic bifunctional (meth)acrylic acid esters, aliphatic bifunctional (meth)acrylic acid esters, trifunctional or higher (Meth) acrylic acid ester, polyfunctional (meth) acrylamide having two or more polymerizable groups, and other polymerizable monomers other than hydrophilic monofunctional polymerizable monomers You can stay. The monomer (b) having no acidic group exhibits the effects of the present invention more remarkably. At least one selected from the group consisting of functional (meth)acrylic acid esters and trifunctional or higher (meth)acrylic acid esters, polyfunctional (meth)acrylamide having two or more polymerizable groups described above , and the hydrophilic monofunctional polymerizable monomer described above.

Although the content of the monomer (b) not having an acidic group is not particularly limited, it improves the curability and adhesiveness of the cured product, and also improves the mechanical strength of the resulting cured product. It is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, relative to 100 parts by mass of all monomers contained in the composite resin for use. , is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and even more preferably 95 parts by mass or less.

・Vanadium compound (c)
Vanadium compounds (c) have conventionally been used as reducing agents for redox polymerization in dental adhesives and the like, and have been used in combination with oxidizing agents such as persulfates. , in particular vanadium compounds (c) are used under conditions substantially free of persulfates. This makes it possible to obtain a dental composite resin that is excellent in storage stability and adhesiveness and that can suppress discoloration of the cured product.

The type of vanadium compound (c) used in the present invention is not particularly limited, but IV- and/or V-valent vanadium compounds are preferred because the effects of the present invention are exhibited more remarkably. , divanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis It is more preferably at least one selected from the group consisting of (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V) and ammonium metavanadate (V), vanadyl acetylacetonate ( IV), bis(maltrate)oxovanadium (IV) is more preferred, and vanadyl acetylacetonate (IV) is particularly preferred. The vanadium compound (c) may be used alone or in combination of two or more.

Although there is no particular limitation on the content of the vanadium compound (c), all units contained in the dental composite resin of the present invention can be It is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, still more preferably 0.01 parts by mass or more, and 0.07 parts by mass with respect to 100 parts by mass of the polymer. It is particularly preferably at least 0.12 parts by mass, and may be at least 0.17 parts by mass. In addition, since it is possible to suppress the elution of unnecessary substances from the obtained cured product, the content of the vanadium compound (c) is , preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less.

- Photoinitiator (d)
The photoinitiator accelerates the polymerization hardening of the dental composite resin. As the photopolymerization initiator (d), photopolymerization initiators used in general industry can be used, and photopolymerization initiators used for dental applications can be preferably used. A photoinitiator (d) may be used individually by 1 type, and may use 2 or more types together.

Examples of the photopolymerization initiator (d) include (bis)acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, and coumarins. , anthraquinones, benzoin alkyl ethers, α-aminoketones and the like.

Among these photopolymerization initiators (d), at least one selected from the group consisting of (bis)acylphosphine oxides (including salts), α-diketones and coumarins is preferred. As a result, it is possible to obtain a dental composite resin that exhibits excellent photocuring properties in the visible region and the near-ultraviolet region, and exhibits sufficient photocuring property using any light source such as a halogen lamp, a light-emitting diode (LED), or a xenon lamp. .

Among the (bis)acylphosphine oxides, acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine. oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethyl phenyl) phosphonates and the like.

Among the (bis)acylphosphine oxides, the bisacylphosphine oxides include, for example, bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenyl Phosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and the like.

The (bis)acylphosphine oxides may be water-soluble (bis)acylphosphine oxides. Examples of the water-soluble acylphosphine oxides include salts of (bis)acylphosphine oxides as exemplified above. Examples of the salt include alkali metal salts such as sodium salts, potassium salts, and lithium salts; alkaline earth metal salts; pyridinium salts; and ammonium salts. Water-soluble (bis)acylphosphine oxides can be synthesized, for example, by the methods disclosed in European Patent No. 0009348, JP-A-57-197289, and the like.

Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine The sodium salt of the oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide is preferred, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is more preferred.

Examples of the α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. be done. Among these, camphorquinone is 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-thienylcoumarin, 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-nitro benzoyl)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′-carbonyl Bis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzo imidazoyl)-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 and the like. Among these, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are preferred.

The content of the photopolymerization initiator (d) is not particularly limited, but since a dental composite resin having excellent adhesion and curability can be obtained, all monomers contained in the dental composite resin of the present invention With respect to 100 parts by mass, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and 0.1 parts by mass It is particularly preferable that it is above. In addition, since a dental composite resin having excellent adhesiveness can be obtained and precipitation from the dental composite resin can be suppressed, the content of the photopolymerization initiator (d) is It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less based on 100 parts by mass of the total monomers contained in the resin.

The dental composite resin of the present invention may further contain a chemical polymerization initiator. Examples of chemical polymerization initiators include organic peroxides such as ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters and peroxydicarbonates. A chemical polymerization initiator may be used individually by 1 type, and may use 2 or more types together. However, from the viewpoint of further improving the storage stability of the dental composite resin and the effect of suppressing discoloration of the resulting cured product, the dental composite resin preferably does not substantially contain an organic peroxide. The content of the organic peroxide in the dental composite resin of the present invention can be, for example, less than 1000 mass ppm, preferably less than 100 mass ppm, relative to the mass of the dental composite resin. , more preferably less than 10 mass ppm, more preferably less than 1 mass ppm, particularly preferably less than 0.1 mass ppm, and most preferably 0 mass ppm.

・Filler (e)
The filler (e) can improve the strength of the dental composite resin as a matrix, and can improve the operability of the dental composite resin. As the filler (e), known fillers used in dental composite resins can be used without any limitation. Fillers can generally be broadly classified into organic fillers, inorganic fillers and organic-inorganic composite fillers (fillers containing inorganic fillers and polymerizable monomers). A filler (e) may be used individually by 1 type, and may use 2 or more types together. Examples of the combined use of two or more types include combined use of fillers having different materials, particle size distributions, forms, and the like. A commercial item can be used as a filler (e). An inorganic filler is preferred as the filler (e).

Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, Polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer and the like. An organic filler may be used individually by 1 type, and may use 2 or more types together. The shape of the organic filler is not particularly limited. The average particle size of the organic filler is preferably 0.0005 to 50 μm, more preferably 0.001 to 10 μm, from the viewpoint of the operability of the obtained dental composite resin and the mechanical strength of the cured product. more preferred.

Examples of 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, Glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. mentioned. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

The shape of the inorganic filler is not particularly limited, and may be appropriately selected according to the properties desired to be enhanced in the dental composite resin. Specifically, it can be used as a powder of amorphous or spherical particles. The use of an amorphous inorganic filler improves the mechanical strength and abrasion resistance of the resulting cured product, and the use of a spherical inorganic filler improves the abrasive lubricity and lubricity durability of the resulting cured product. improves.

The average particle size of the inorganic filler is preferably 0.001 to 50 μm, more preferably 0.005 to 20 μm, from the viewpoint of the operability of the resulting dental composite resin and the mechanical strength of the resulting cured product. is more preferably 0.008 to 10 μm, particularly preferably 0.01 to 5 μm, and may be 0.02 to 1 μm. In this specification, the average particle size of the filler (e) means the average particle size (average primary particle size) of the primary particles of the filler (e). As the average particle size of the filler (e), the filler (e) is dispersed in a dispersion medium consisting of at least one selected from alcohol and water, and is subjected to a laser diffraction method such as "SALD-2300" manufactured by Shimadzu Corporation. The median value of the volume particle size distribution measured with a particle size distribution analyzer can be used. If the average particle size of the filler (e) is small and is below the lower limit of measurement (for example, 0.10 μm) in the laser diffraction particle size distribution measuring device, such as “SU3500” or “SU9000” manufactured by Hitachi, Ltd. Electron micrographs can be taken using a scanning electron microscope and the mean value obtained from the particle sizes of 20 randomly selected particles can be taken. When the particles are non-spherical, the particle diameter may be the arithmetic mean of the longest and shortest lengths of the particles.

The inorganic filler may be aggregated particles formed by aggregation of particles. Usually, commercially available inorganic fillers exist as aggregates, but 10 mg of inorganic filler powder is added to 300 mL of water (dispersion medium) to which a surfactant such as water or 5% by mass or less of sodium hexametaphosphate is added, When dispersed for 30 minutes at an ultrasonic intensity of 40 W output and a frequency of 39 KHz, it has only a weak cohesive force to the extent that it can be dispersed to the particle size indicated by the manufacturer. However, the aggregated particles are strongly aggregated particles that are hardly dispersed even under such conditions.

As a method for producing agglomerated particles in which particles are strongly agglomerated from commercially available inorganic filler agglomerates, the inorganic filler particles are heated to a temperature just before they melt, and the inorganic filler particles that come into contact are slightly fused together. A method of heating to the extent that the In this case, in order to control the shape of the aggregated particles, the particles may be aggregated before heating. Examples of the method include a method in which the inorganic filler is placed in a suitable container and pressurized, a method in which the inorganic filler is once dispersed in a solvent, and then the solvent is removed by a method such as spray drying.

In addition, as another suitable method for producing aggregated particles, a sol such as silica sol, alumina sol, titania sol, zirconia sol, etc. produced by a wet method is used, and this is dried by a method such as freeze drying or spray drying, A method of heat treatment may be mentioned as necessary. Specific examples of the sol include those manufactured by Nippon Shokubai Co., Ltd. under the trade name of "Seahoster", manufactured by JGC Catalysts & Chemicals Co., Ltd. under the trade names of "OSCAL" and "QUEEN TITANIC", and manufactured by Nissan Chemical Industries, Ltd. under the trade name of "Snowtex". , “Aluminasol”, “Celnax”, “Nanouse” and the like.

The inorganic filler is used to improve the affinity with the monomers contained in the dental composite resin of the present invention, and to improve the mechanical strength of the cured product by increasing chemical bonding with the monomers. In addition, it is desirable to apply a surface treatment with a surface treatment agent in advance. Examples of the surface treatment agent include organic silicon compounds, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds. One of these surface treatment agents may be used alone, or two or more thereof may be used in combination. When two or more types of surface treatment agents are used in combination, the surface treatment layer formed by such surface treatment agents may be a surface treatment layer of a mixture of two or more surface treatment agents, or may have a multi-layer structure in which a plurality of surface treatment layers are laminated. It may be a surface treatment layer. As the surface treatment method, a known method can be used without any particular limitation.

Examples of organosilicon compounds include compounds represented by R ⁹ _n SiX _4-n (wherein R ⁹ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, X is a carbon number 1 to 4 alkoxy groups, acetoxy groups, hydroxyl groups, halogen atoms or hydrogen atoms, and n is an integer of 0 to 3. However, when there are multiple R ⁹ and X, they are the same. may be different).

Specific examples of organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxy propylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, N-(β-aminoethyl)γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)γ-aminopropyltrimethoxysilane, N-( β-aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethyl Silanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω-(meth)acryloyloxyalkyltri Methoxysilane (number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12, e.g., γ-methacryloyloxypropyltrimethoxysilane, etc.), ω-(meth)acryloyloxyalkyltriethoxysilane ((meth)acryloyloxyalkyltriethoxysilane ((meth) ) Number of carbon atoms between acryloyloxy group and silicon atom: 3 to 12, e.g., γ-methacryloyloxypropyltriethoxysilane, etc.), organosilazanes (hexaethyldisilazane, hexan-propyldisilazane, hexaisopropyldisilazane , 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,1 , 1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane, etc.).

Among these, an organosilicon compound having a functional group capable of copolymerizing with the monomer contained in the dental composite resin of the present invention is preferred. Preferred specific examples of organosilicon compounds include ω-(meth)acryloyloxyalkyltrimethoxysilane (the number of carbon atoms between the (meth)acryloyloxy group and the silicon atom: 3 to 12), ω-(meth)acryloyloxyalkyl triethoxysilane (number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, Organosilazanes (1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane, etc.) be.

Examples of organic titanium compounds include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra(2-ethylhexyl) titanate.

Examples of organic zirconium compounds include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconium acetate and the like.

Examples of organic aluminum compounds include aluminum acetylacetonate and aluminum organic acid salt chelate compounds.

As the organic-inorganic composite filler, inorganic particles having an average particle size of 0.5 μm or less are preferably dispersed in an organic matrix, and the production method is not particularly limited. For example, after previously adding a known polymerizable monomer and a known polymerization initiator to the inorganic filler and making it into a paste, it is polymerized by a polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization, It can be made by pulverizing.

The average particle size of the organic-inorganic composite filler is preferably 1-50 μm, more preferably 3-25 μm. When the average particle size of the organic-inorganic composite filler is at least the above lower limit, the stickiness of the obtained dental composite resin can be further reduced and the operability is improved. Further, when the average particle size of the organic-inorganic composite filler is equal to or less than the above upper limit, the obtained dental composite resin can be suppressed from being rough and dry, and the operability is also improved.

The content of the filler (e) is not particularly limited, but from the viewpoint of the operability of the obtained dental composite resin and the mechanical strength of the cured product, all the monomers contained in the dental composite resin of the present invention are 100 It is preferably 100 parts by mass or more, more preferably 130 parts by mass or more, still more preferably 150 parts by mass or more, and preferably 900 parts by mass or less, It is more preferably 600 parts by mass or less, even more preferably 450 parts by mass or less, and particularly preferably 200 parts by mass or less.

In the dental composite resin of the present invention, the monomer (a) having an acidic group, the monomer (b) having no acidic group, the vanadium compound (c), the photopolymerization initiator (d) and the filler ( The total content of e) can be appropriately changed according to the usage form and purpose of the dental composite resin of the present invention. % or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, 98% by mass or more, 99% by mass or more, and even 100% by mass. .

Optional components The dental composite resin of the present invention comprises the above-described monomer having an acidic group (a), monomer having no acidic group (b), vanadium compound (c), and photopolymerization initiator (d). and the filler (e) alone, but may further contain one or more of other optional components. Examples of such optional components include polymerization accelerators, polymerization inhibitors, fluoride ion-releasing substances, pH adjusters, ultraviolet absorbers, thickeners, colorants, antibacterial agents, fragrances, and the like.

(Polymerization accelerator)
The polymerization accelerator can accelerate the polymerization and curing of the dental composite resin together with the photopolymerization initiator (d). As the polymerization accelerator, known polymerization accelerators can be used, for example, amines, sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, halogen compounds, Aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds and the like can be mentioned, and amines are preferred. One of the polymerization accelerators may be used alone, or two or more thereof may be used in combination.

Said amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; ; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono tertiary aliphatic amines such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine and tributylamine; Among these, tertiary aliphatic amines are preferred, and N-methyldiethanolamine and triethanolamine are more preferred, from the viewpoint of the curability and storage stability of the dental composite resin.

Examples of the aromatic amine 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)methyl benzoate , 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 and ethyl 4-(N,N-dimethylamino)benzoate are used because they can impart excellent curability to dental composite resins. , 4-(N,N-dimethylamino)benzoate n-butoxyethyl and 4-(N,N-dimethylamino)benzophenone are preferred, and 4-(N,N-dimethylamino)ethyl benzoate is more preferred.

Specific examples of the sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogensulfites, and thiourea compounds , for example, those described in International Publication No. 2008/087977.

The content of the polymerization accelerator is not particularly limited. On the other hand, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and 0.1 parts by mass or more is particularly preferred. In addition, the content of the polymerization accelerator is included in the dental composite resin of the present invention because a dental composite resin having excellent adhesiveness can be obtained and precipitation from the dental composite resin can be suppressed. It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of the total monomers. is particularly preferred.

(Polymerization inhibitor)
Examples of polymerization inhibitors include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, hydroquinone monomethyl ether, 2,6-di-t-butylphenol and the like. . A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.

The content of the polymerization inhibitor is not particularly limited, but since the desired effect can be obtained, it is 0.001 parts by mass or more with respect to 100 parts by mass of all the monomers contained in the dental composite resin of the present invention. is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, particularly preferably 0.05 parts by mass or more, and 10 parts by mass is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less.

(Fluoride ion-releasing substance)
When the dental composite resin contains a fluoride ion-releasing substance, acid resistance can be imparted to the dentin. Examples of such fluoride ion-releasing substances include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. Fluoride ion-releasing substances may be used singly or in combination of two or more.

• Persulfates The dental composite resin of the present invention is substantially free of persulfates (preferably peroxides). As a result, it is possible to obtain a dental composite resin that not only has excellent adhesiveness, but also has excellent storage stability and can suppress discoloration of the cured product. Such a dental composite resin can be obtained, for example, by not blending a persulfate (preferably a peroxide).

Examples of the persulfate include those described in Patent Document 3, and may be a water-soluble one dissociated into ions. More specific examples include Na ₂ S ₂ O ₈ , K ₂ S ₂ O ₈ , (NH ₄ ) ₂ S ₂ O ₈ and the like.

The content of persulfate (preferably peroxide) in the dental composite resin of the present invention can be, for example, less than 1000 ppm by mass, and less than 100 ppm by mass relative to the mass of the dental composite resin. Preferably, it is less than 10 mass ppm, more preferably less than 1 mass ppm, particularly preferably less than 0.1 mass ppm, and most preferably 0 mass ppm. .

・Form of dental composite resin There is no particular limitation on the form of the dental composite resin of the present invention, and it may be either a single material type or a divided package type, but it is easy to operate and is preferable as a dental composite resin. A single-material type is preferable because it can be used.

[Preparation method]
The method for preparing the dental composite resin of the present invention is not particularly limited, and it can be obtained by blending the respective components described above. The order of blending is not particularly limited, and each component may be blended together or may be blended in two or more batches.

〔how to use〕
The method of using the dental composite resin of the present invention is not particularly limited, and it can be preferably used for filling a cavity. It can be used for filling a dental composite resin and then curing the filled dental composite resin by irradiating it with visible light. In particular, the dental composite resin of the present invention can be preferably used as a self-adhesive dental composite resin. The dental composite resin of the present invention can be used by filling directly into a cavity or the like.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Raw materials used in the following examples and comparative examples are shown below.

[Monomer (a) having an acidic group]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate 4-META: acid anhydride of 4-methacryloyloxyethyl trimellitate

[Monomer (b) not having an acidic group]
- Aromatic bifunctional (meth) acrylic acid ester Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D-2.6E: 2,2 -Bis(4-methacryloyloxypolyethoxyphenyl)propane (with an average number of added moles of ethoxy groups of 2.6)

・Aliphatic bifunctional (meth)acrylic acid ester UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate TEGDMA: triethylene glycol dimethacrylate

- Polyfunctional (meth)acrylamide TAC4 having two or more polymerizable groups: N,N',N'',N'''-tetraacryloyltriethylenetetramine (compound (iv-1-5))
MAEA: N-methacryloyloxyethyl acrylamide (compound (iv-3-1))

・Hydrophilic monofunctional polymerizable monomer HEMA: 2-hydroxyethyl methacrylate DEAA: N,N-diethylacrylamide

[Vanadium compound (c)]
VOAA: vanadyl acetylacetonate (IV)
BMOV: bis(maltrate)oxovanadium(IV)

[Copper compound]
CuAA: copper (II) acetate

[Persulfate]
KPS: potassium persulfate

[Photoinitiator (d)]
CQ: dl-camphorquinone BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[Filler (e)]
Filler (e-1):
The one produced in Production Example 1 below was used.

Filler (e-2):
The one produced in Production Example 2 below was used.

R7200:
Commercial product (trade name “AEROSIL R7200” manufactured by EVONIK INDUSTRIES, surface treatment agent: silane compound containing methacryloyloxysilyl group, BET specific surface area: 145 m ² /g, average primary particle size: 12 nm, pH: 4.5, apparent Specific gravity: 230 g/L) was used as it was.

R711:
Commercially available product (trade name “AEROSIL R711” manufactured by EVONIK INDUSTRIES, surface treatment agent: silane compound containing methacryloyloxysilyl group, BET specific surface area: 150 m ² /g, average primary particle size: 12 nm, pH: 4.5, apparent Specific gravity: 50 g/L) was used as it was.

YBF:
A commercially available product (manufactured by Sukgyung AT, trade name “SG-YBF100WSCMP10” (silica-coated ytterbium fluoride), average particle size: 110 nm, spherical particles) was used as it was.

ALU-C:
A commercially available product (trade name “AEROXIDE Alu C” manufactured by EVONIK INDUSTRIES, BET specific surface area: 100 m ² /g, average primary particle size: 13 nm, pH: 5.0, apparent specific gravity: 50 g/L) was used as it was.

ST-ALU-C:
A commercially available product (EVONIK INDUSTRIES trade name “AEROXIDE Alu C”, BET specific surface area: 100 m ² /g, average primary particle size: 13 nm, pH: 5.0, apparent specific gravity: 50 g / L), 10-methacryloyl A surface treated with oxydecyldihydrogen phosphate and 11-methacryloyloxyundecyltrimethoxysilane was used.

[Polymerization accelerator]
DABE: 4-(N,N-dimethylamino) ethyl benzoate [polymerization inhibitor]
BHT: 3,5-di-t-butyl-4-hydroxytoluene

[Production Example 1]
・ Production of filler (e-1) Silica particles (trade name “Snowtex OL” manufactured by Nissan Chemical Industries, Ltd., colloidal silica, aqueous dispersion with solid content concentration of 20% by mass, average particle size: 50 nm) 100 parts by mass 60 parts by mass of isopropanol was added to and mixed at room temperature (about 25° C.) to obtain a dispersion. To this dispersion, 0.48 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (trade name “KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) and a polymerization inhibitor (3,5-di- manufactured by Kanto Chemical Co., Ltd.) 0.01 part by mass of t-butyl-4-hydroxytoluene (BHT)) was added and mixed at 40° C. for 72 hours. Then, 0.78 part by mass of 1,1,1,3,3,3-hexamethyldisilazane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "HMDS-1") was added to the mixture and allowed to stand at 40°C for 72 hours. bottom. In this process, the surface treatment of the silica particles progressed, and the silica particles that had become hydrophobic could no longer exist stably in water and isopropanol, and aggregated and precipitated. 2.6 parts by mass of a 35% hydrochloric acid aqueous solution was added to the total amount of the mixture obtained after the surface treatment to precipitate silica particles. The precipitate was filtered with filter paper (5A manufactured by Advantech). The filtration residue (solid content) was washed with pure water and then vacuum-dried at 100° C. to obtain a filler (e-1).

[Production Example 2]
Production of filler (e-2) Except for changing the amount of 1,1,1,3,3,3-hexamethyldisilazane used in Production Example 1 from 0.78 parts by mass to 2.8 parts by mass. A filler (e-2) was obtained in the same manner as in Production Example 1.

[Examples 1 to 25 and Comparative Examples 1 to 4]
Using the raw materials described above, among the components listed in Tables 1 to 3, the components other than the filler (e) are mixed at room temperature to form a uniform liquid component, and the obtained liquid component and the filler (e) are mixed at room temperature. ) were kneaded to prepare dental composite resins of Examples 1 to 25 and Comparative Examples 1 to 4, respectively. Next, using these dental composite resins, the decomposition of the photopolymerization initiator, the curing depth, the adhesiveness to dentin, the bending strength of the cured product, and the discoloration of the cured product were measured or evaluated according to the methods described below. These results are shown in Tables 1 to 3.

-Decomposition of Photopolymerization Initiator The dental composite resin obtained in each Example or Comparative Example was filled in a light-shielding container and stored in a thermostat at 50°C for 3 weeks. The dental composite resin after storage was irradiated with light for 10 seconds using a dental visible light irradiator (trade name “Pencure 2000” manufactured by Morita Co., Ltd.), and the cured state was checked by pressing with a slide glass. confirmed. Those that retained their shape even when pressure-contacted were evaluated as "○", and those that lost their shape even a little and remained uncured (probably due to the decomposition of the photopolymerization initiator) were evaluated as "X". evaluated.

-Cure depth Measured according to ISO4049:2000.

- Adhesiveness to dentin The lip surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample in which the flat surface of the dentin was exposed. The obtained sample was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape having a thickness of about 150 μm and having a round hole with a diameter of 3 mm was adhered to the smooth surface after drying to define the adhesion area.
The dental composite resin obtained in each example or comparative example was filled in the round hole and covered with a release film (polyester). Next, a slide glass was placed on the release film and pressed to smooth the coated surface of the dental composite resin. Subsequently, the dental composite resin was irradiated with light for 10 seconds using a dental visible light irradiator (trade name “Pencure 2000” manufactured by Morita Co., Ltd.) through the release film. Cure the composite resin.
A commercially available dental resin cement (trade name “Panavia 21” manufactured by Kuraray Noritake Dental Co., Ltd.) was applied to the surface of the cured dental composite resin obtained, and a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) was glued on one end face (circular cross section). After adhesion, the sample was allowed to stand at room temperature for 30 minutes, and then immersed in distilled water to obtain an adhesion test sample. Five test samples for the adhesion test were prepared and allowed to stand in a thermostatic chamber maintained at 37°C for 24 hours.
The tensile bond strength of the test sample for the above bond test was measured using a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100 kN") with the crosshead speed set to 2 mm/min. The average value was obtained as the tensile adhesive strength, which was used as an index of adhesiveness to dentin.

- Bending strength of cured product It was measured according to ISO4049:2000.

Discoloration of Cured Product The dental composite resin obtained in each Example or Comparative Example was filled in a stainless steel mold (15 mmφ×1 mm). The upper and lower surfaces of the slide glass were pressed against each other, and a dental visible light irradiator (trade name "Pencure 2000" manufactured by Morita Co., Ltd.) was used to apply light to both surfaces of the slide glass at 5 points per point for 10 seconds. It was irradiated and cured to prepare a disk-shaped specimen of the cured product.
For the disc-shaped test piece, using a spectrophotometer (trade name "CM-3610d" manufactured by Konica Minolta Japan Co., Ltd.), a D65 light source, a colorimetric field of view of 2 degrees, and a standard white plate behind the disc-shaped test piece. and measured the chromaticity. The chromaticity was measured immediately after the disk-shaped test piece was prepared and after the disk-shaped test piece was stored in water at 37°C ^for one week. was calculated. A smaller value of ΔE ^* means less discoloration of the cured product. ΔE ^* =less than 4 was evaluated as “◯”, and 4 or more was evaluated as “×”.

As shown in Tables 1 to 3, the dental composite resins (Examples 1 to 25) according to the present invention are excellent in storage stability because decomposition of the photopolymerization initiator is suppressed, and the resulting cured products are free from discoloration. It can be seen that it is suppressed and exhibits excellent discoloration resistance. Moreover, although it does not contain a persulfate, it exhibits a high tensile adhesive strength of 11.1 MPa or more to dentin, indicating excellent adhesiveness.
On the other hand, the dental composite resins containing persulfate (Comparative Examples 1 and 4) were excellent in adhesiveness, but were inferior in both storage stability and discoloration resistance in cured products. Moreover, in Comparative Example 2 in which a copper compound was used instead of the vanadium compound, the adhesiveness was poor.

Claims (8)

a monomer having an acidic group (a), a monomer having no acidic group (b), a vanadium compound (c), a photopolymerization initiator (d) and a filler (e), persulfate and hydroperoxide substantially free of
The hydroperoxide content is less than 100 mass ppm,
Composite resin for dentistry , which is a single material type . 2. The dental composite resin according to claim 1, wherein the vanadium compound (c) is a IV-valent and/or V-valent vanadium compound. The vanadium compound (c) is divanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis(1-phenyl-1,3-butanedionate). ) is at least one selected from the group consisting of vanadium (IV), bis(maltrate)oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V) and ammonium metavanadate (V). 2. The dental composite resin according to 1. The dental composite resin according to any one of claims 1 to 3, wherein the content of the vanadium compound (c) is 0.001 to 10 parts by mass with respect to 100 parts by mass of all the monomers. Claims 1 to 4, wherein the monomer (a) having an acidic group is a (meth)acrylic monomer having a phosphoric acid group and/or a (meth)acrylic monomer having a carboxylic acid group. The dental composite resin according to any one of 1. The dental composite resin according to any one of claims 1 to 4, wherein the monomer (a) having an acidic group is a (meth)acrylic monomer having a phosphoric acid group. The dental product according to any one of claims 1 to 6, wherein the content of the monomer (a) having an acidic group is 1 to 40 parts by mass with respect to 100 parts by mass of the total monomers. composite resin. The dental composite resin according to any one of claims 1 to 7, wherein the content of said filler (e) is 100 to 900 parts by mass with respect to 100 parts by mass of all monomers.