JP7105063B2 - Polymerizable monomer suitable for dental material and dental composition using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable monomer, a dental composition containing the polymerizable monomer, and a dental composite resin comprising the dental composition.

Conventionally, radically polymerizable monomers represented by (meth)acrylic acid esters have been used in various fields such as paints, printing plates, optical materials, dental materials, etc., by utilizing their properties such as good curability and transparency. widely used in

Among them, in the field of dental materials, radically polymerizable monomers are used in dental restoration materials typified by dental composite resins used for restoration of caries, fractures, etc. of natural teeth, and dental composite resins and teeth. It is widely used for various dental adhesives used for bonding, artificial teeth, denture base materials, and the like.

In particular, dental composite resins have come to be widely used in recent years in place of conventionally used metal materials because of their esthetic properties close to those of natural teeth and excellent operability. Dental composite resins are generally composed mainly of a polymerizable monomer, a polymerization initiator, and a filler. Radically polymerizable polyfunctional (meth)acrylates are used from the viewpoint of abrasion resistance. Among them, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA) and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate ( UDMA) is widely used. Moreover, since Bis-GMA and UDMA have high viscosity when used alone, they are generally diluted with a relatively low-viscosity monomer such as triethylene glycol dimethacrylate (3G) before use.

Although dental composite resins have come to be widely used clinically today, improvements are desired in the following points. In other words, improved bending strength, elastic modulus, and abrasion resistance of the cured product, reduced water absorption and discoloration, reduced polymerization shrinkage during curing, a coefficient of thermal expansion close to that of natural teeth, and transparency and It has been pointed out that there is still much room for improvement in terms of esthetics and the like.

Furthermore, in recent years, there has been an increasing demand for easy handling of dental materials, that is, operability. Being able to fill is important.

Polymerization shrinkage causes the generation of contraction gaps caused by peeling of the dental composite resin from the bonding surface, and therefore it is strongly desired to reduce it as much as possible. The occurrence of contraction gaps causes secondary caries, pulp irritation, discoloration, loss of restorations, and the like. In addition, since there is a large difference in the coefficient of thermal expansion between the dental composite resin and the tooth substance, when heat history is applied in the oral cavity, the gap between the dental composite resin and the tooth substance tends to separate and create a gap. It causes subsequent caries, pulp irritation, discoloration, and detachment of restorations.

In addition, high bending strength is desired from the viewpoint of durability (impact resistance and fracture resistance) in the oral cavity. In general, inorganic particles are blended as a means of imparting strength, but when inorganic particles are blended, the toughness tends to decrease and the material tends to be brittle and break easily. In order to achieve both strength and toughness, and also to impart aesthetic properties such as polishability and luster, there has been a tendency to use smaller inorganic particles as fillers. However, when inorganic particles having a small particle size are blended, the problem is that the viscosity rises, making it difficult to extrude, and the operability deteriorates. Also, 3G is generally blended as a diluent monomer as a means of lowering the viscosity, but due to the effect of 3G, polymerization shrinkage during curing is large. An object of the present invention is to provide a dental composite resin with low viscosity and small polymerization shrinkage.

The following techniques are known as techniques that are excellent in such mechanical properties, aesthetics and operability. Patent Document 1 reports a dental composition in which polymerization shrinkage and aesthetics are improved by containing a methacrylic monomer containing a silicon-aryl bond, but a monomer having a sufficiently low viscosity cannot be obtained. There is a problem. Further, Patent Document 2 reports a dental composition in which polymerization shrinkage, aesthetics and strength are improved by containing an adamantane derivative, but the problem is that a monomer having a sufficiently low viscosity cannot be obtained. There is Further, Patent Document 3 reports a dental composition improved in polymerization shrinkage, aesthetics and strength by containing a methacrylic monomer containing a silicon-aryl bond and a silicon-oxygen bond. There is a problem that a dental composition cannot be obtained.

Japanese Patent Publication No. 2008-505939 JP-A-2009-84221 JP 2009-179595 A

The present invention provides a polymerizable monomer useful for dental composite resins, which has small polymerization shrinkage during curing, excellent operability, excellent mechanical strength of the cured product, and a coefficient of thermal expansion close to that of natural teeth. intended to provide

｛式中、Ｒ¹～Ｒ⁴はそれぞれ独立に、炭素数１～２０の炭化水素基（但しＲ¹～Ｒ⁴はいずれもケイ素原子を含まない）であり、Ｘ¹及びＸ²はそれぞれ独立に、（メタ）アクリロキシ基、又は（メタ）アクリルアミド基である｝
で表される重合性単量体；
［２］２５℃における粘度が１０００ｃＰ以下である、前記［１］に記載の重合性単量体；
［３］Ｒ¹及びＲ²がそれぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基（但しＲ¹及びＲ²はいずれもケイ素原子を含まない）である、前記［１］又は［２］に記載の重合性単量体；
［４］Ｒ¹及び／又はＲ²が置換基を有していてもよいフェニル基である、前記［１］～［３］のいずれかに記載の重合性単量体；
［５］Ｒ¹及びＲ²の少なくとも１つは置換基を有さないフェニル基である、前記［４］に記載の重合性単量体；
［６］Ｒ¹及びＲ²がそれぞれ独立に、置換基を有していてもよい炭素数１～２０の脂肪族炭化水素基（但しＲ¹及びＲ²はいずれもケイ素原子を含まない）である、前記［１］～［３］のいずれかに記載の重合性単量体；
［７］Ｒ³及びＲ⁴がそれぞれ独立に、置換基を有していてもよい炭素数１～２０の２価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数６～２０の２価の芳香族炭化水素基（但しＲ³及びＲ⁴はいずれもケイ素原子を含まない）である、前記［１］～［６］のいずれかに記載の重合性単量体；
［８］Ｒ³及びＲ⁴がそれぞれ独立に、置換基を有していてもよい炭素数１～２０の２価の脂肪族炭化水素基（但しＲ³及びＲ⁴はいずれもケイ素原子を含まない）である、前記［１］～［７］のいずれかに記載の重合性単量体；
［９］Ｒ³及びＲ⁴の少なくとも１つは置換基を有さない脂肪族炭化水素基である、前記［７］又は［８］に記載の重合性単量体；
［１０］前記［１］～［９］のいずれかに記載の重合性単量体を含む歯科用組成物；
［１１］さらに、重合開始剤及びフィラーを含む、前記［１０］に記載の歯科用組成物；
［１２］前記［１０］又は［１１］のいずれかに記載の歯科用組成物からなる歯科用コンポジットレジン；
に関する。 The above object is solved by providing a compound represented by the following general formula (1).
That is, the present invention
[1] General formula (1) below

{wherein R ¹ to R ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms (provided that none of R ¹ to R ⁴ contains a silicon atom), and X ¹ and X ² are each independently is a (meth) acryloxy group or a (meth) acrylamide group}
A polymerizable monomer represented by;
[2] The polymerizable monomer according to [1] above, which has a viscosity of 1000 cP or less at 25°C;
[3] R ¹ and R ² are each independently an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted carbon number of 6 The polymerizable monomer according to [1] or [2] above, which is a monovalent aromatic hydrocarbon group of up to 20 (provided that neither R ¹ nor R ² contains a silicon atom);
[4] The polymerizable monomer according to any one of [1] to [3] above, wherein R ¹ and/or R ² is a phenyl group which may have a substituent;
[5] The polymerizable monomer according to [4] above, wherein at least one of R ¹ and R ² is an unsubstituted phenyl group;
[6] R ¹ and R ² are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms (provided that neither R ¹ nor R ² contains a silicon atom); The polymerizable monomer according to any one of [1] to [3];
[7] R ³ and R ⁴ are each independently an optionally substituted C 1-20 divalent aliphatic hydrocarbon group, or an optionally substituted C 6 The polymerizable monomer according to any one of [1] to [6] above, which is a divalent aromatic hydrocarbon group of up to 20 (provided that neither R ³ nor R ⁴ contains a silicon atom);
[8] R ³ and R ⁴ are each independently an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (provided that both R ³ and R ⁴ contain a silicon atom; not), the polymerizable monomer according to any one of [1] to [7];
[9] The polymerizable monomer according to [7] or [8] above, wherein at least one of R ³ and R ⁴ is an unsubstituted aliphatic hydrocarbon group;
[10] A dental composition comprising the polymerizable monomer according to any one of [1] to [9];
[11] The dental composition according to [10] above, further comprising a polymerization initiator and a filler;
[12] A dental composite resin comprising the dental composition according to any one of [10] or [11];
Regarding.

The polymerizable monomer of the present invention is characterized by excellent mechanical strength of the cured product and small polymerization shrinkage during polymerization and curing. Therefore, it is suitable for dental compositions, especially dental composite resins for treating carious cavities. A dental material such as a dental composite resin using a dental composition containing the polymerizable monomer of the present invention has excellent durability in the oral cavity and a contraction gap between the dental material and the adhesive surface. It is less likely to occur, and concerns such as secondary caries, pulpal irritation, and detachment of restorations are reduced. Moreover, since the polymerizable monomer of the present invention has a low viscosity, the dental composition containing the polymerizable monomer of the present invention has excellent operability. Furthermore, the dental composition containing the polymerizable monomer of the present invention reduces the risk of detachment between the dental composition and the dentin when heat history is applied in the oral cavity.

The details of the present invention will be described below.

The polymerizable monomer of the invention is a compound represented by the following general formula (1). From the viewpoint of obtaining a low-viscosity polymerizable monomer, in the formula, R ¹ to R ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms (provided that R ¹ to R ⁴ all contain a silicon atom). not). That is, R ¹ , R ² , R ³ and R ⁴ do not all contain a silicon atom at the same time, and consequently the compound represented by general formula (1) has only one silicon atom. For hydrocarbon groups having 1 to 20 carbon atoms, R ¹ and R ² are monovalent hydrocarbon groups and R ³ and R ⁴ are divalent hydrocarbon groups.

Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ and R ² include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms. From the viewpoint of improving the strength of the cured product and suppressing polymerization shrinkage during polymerization and curing, it is preferable that each of R ¹ and R ² independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the monovalent hydrocarbon group represented by R ¹ and R ² is preferably 1-15, more preferably 1-11.

The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² may be linear, branched, or cyclic. methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, aliphatic saturated hydrocarbon groups such as various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various eicosyl groups ; cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl group, cyclooctyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl monocyclic alicyclic hydrocarbon groups having 3 to 20 carbon atoms such as a cycloeicosyl group; polycyclic carbon atoms such as groups represented by the following general formulas (a-1) to (a-8) 7 to 20 alicyclic hydrocarbon groups are included.

The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² may be either saturated or unsaturated .

The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² may or may not have one or more substituents. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, halogenated alkyl groups having 1 to 5 carbon atoms substituted with halogen atoms, hydroxyl groups, carboxyl groups, and amino groups. , an oxygen atom (=O), and the like. The number of substituents may be 1-10, 1-6, or 1-3.

Examples of the monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R ¹ and R ² include phenyl group, biphenylyl group, terphenylyl group, styryl group, naphthyl group, anthryl group, acenaphthenyl group, fluorenyl group and phenanthryl. aryl groups such as groups and indenyl groups; benzyl group, phenethyl group, 1-phenylethyl group, 2-phenylpropyl group, 3-phenylpropyl group, phenylbutyl group, 1-methyl-3-phenylpropyl group, naphthylmethyl group , naphthylethyl group, naphthylpropyl group, naphthylbutyl group, and other aralkyl groups; group, benzoxazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothiophenyl group and other heteroaromatic ring groups. Among them, from the viewpoint of improving the strength of the cured product, suppressing polymerization shrinkage during polymerization and curing, and facilitating the availability of raw materials, R ¹ and / or R ² is a phenyl group which may have a substituent. At least one of R ¹ and R ² is more preferably an unsubstituted phenyl group, and R ¹ and R ² are further an unsubstituted phenyl group preferable.

The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ¹ and R ² may or may not have one or more substituents. The type and number of substituents on the monovalent aromatic hydrocarbon group represented by R ¹ and R ² are the same as the type and number of substituents on the monovalent aliphatic hydrocarbon group represented by R ¹ and R ² .

Among the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ and R ² , methyl group, methoxy group, ethyl group, ethoxy group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, cyclohexyl group, 3-cyclohexenyl group, 4-methoxycyclohexyl group, 2-norbornyl group, isobornyl group, adamantyl group, 1-methyladamantyl group, tricyclo[5.2.1.0(2,6)]decanyl group, morpholino group, phenyl group, tolyl group, benzyl group, phenoxy group, P-methoxyphenyl group, p-methoxybenzyl group and the like are preferred, and methyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, adamantyl group and phenyl group are more preferred.

The divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ³ and R ⁴ is obtained by removing one hydrogen atom from the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² . groups. The number of carbon atoms in the divalent hydrocarbon group represented by R ³ and R ⁴ is preferably 1-15, more preferably 1-11.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ³ and R ⁴ include ethylene group, various propylene groups, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, and various octylene groups. , various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups, various eicosylene groups, etc. C1-C20 divalent aliphatic hydrocarbon groups; Cyclic hydrocarbon group; an alicyclic hydrocarbon group having 7 to 20 carbon atoms consisting of a polycyclic group, such as the groups represented by the above general formulas (a-1) to (a-8), having two bonding sites Cyclic hydrocarbon groups; divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylenes; alkyls such as toluene and ethylbenzene C7-C20 alkyl aromatic hydrocarbon groups having monovalent bonding sites on the alkyl group portion and the aromatic portion of the aromatic hydrocarbon; xylene, diethylbenzene, and other C8-C20 polyalkyl aromatic hydrocarbon groups A polyalkylaromatic hydrocarbon group having a bonding site on the alkyl group portion of hydrogen and the like can be mentioned.

The divalent hydrocarbon groups having 1 to 20 carbon atoms represented by R ³ and R ⁴ may or may not have one or more substituents. The types and number of substituents of the divalent hydrocarbon groups represented by R ³ and R ⁴ are the same as the types and number of substituents of the monovalent aliphatic hydrocarbon groups represented by R ¹ and R ² . In one preferred embodiment, at least one of R ³ and R ⁴ is an unsubstituted aliphatic hydrocarbon group.

Among the divalent hydrocarbon groups having 3 to 20 carbon atoms represented by R ³ and R ⁴ , various propylene groups and various butylene groups are considered in consideration of the availability of raw materials and ease of synthesis. , various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, and the like are preferable.

In the above general formula (1), X ¹ and X ² are each independently a (meth)acryloxy group or a (meth)acrylamide group, and a monomer having high reactivity and stability A methacryloxy group or an acrylamide group is more preferable in terms of availability. Here, the (meth)acryloxy group represents an acryloxy group (b-1) or a methacryloxy group (b-2), and the (meth)acrylamide group represents an acrylamide group (b-3) or a methacrylamide group (b -4). Among them, from the viewpoint of curability, biocompatibility and storage stability, it is preferable to use a methacryloxy group (b-2) or an acrylamide group (b-3) as X ¹ and X ² .

The viscosity of the polymerizable monomer of the present invention at 25° C. is preferably 1000 cP or less, more preferably 500 cP or less, from the viewpoint of the operability of the dental composition containing the polymerizable monomer of the present invention. The viscosity at 25° C. can be measured by the method described in Examples below.

Although the method for producing the polymerizable monomer of the present invention is not particularly limited, a method of synthesizing according to the following scheme, for example, is preferably used in bonding an organic group to a silicon atom. That is, it is a method of bonding a (meth)acrylate-like compound having a terminal unsaturated bond to a dihydrosilane compound having a Si—H group as shown in scheme (I) below by a hydrosilylation reaction.

（式中、Ｒ¹及びＲ²は、上記と同一意味を有し、ＸはＸ¹及びＸ²と同一意味を有し、Ｒ’はＲ³及びＲ⁴の２価の炭化水素基からエチレン基を除いた炭化水素基を表す。）

(wherein R ¹ and R ² have the same meanings as above, X has the same meanings as X ¹ and X ² , and R′ is the divalent hydrocarbon group of R ³ and R ⁴ to ethylene represents a hydrocarbon group excluding the group.)

In scheme (I), the dihydrosilane compound having a Si—H group may be synthesized by a known method or commercially available.

Known methods for synthesizing a dihydrosilane compound having a Si—H group include, for example, D. Straus, et al. Am. Chem. Soc. , 112, 2673-2681 (1990), a starting material having Si—H groups can be obtained by condensing aromatic chlorosilanes in acetonitrile. Further, as described in JP-A-2013-87114, by reducing a dichlorosilane compound having a Si—Cl group in a hydrocarbon solvent using an alkoxyaluminum alkali metal hydride, Si— A dihydrosilane compound having H groups can be obtained.

Moreover, in scheme (I), the reaction conditions for the hydrosilylation reaction are not particularly limited. The organic solvent used in the hydrosilylation reaction is not particularly limited as long as it easily dissolves the starting material without reacting with it. Preferred examples of organic solvents are aliphatic hydrocarbons (eg hexane and heptane), aromatic hydrocarbons (eg toluene and xylene), and cyclic ethers (eg tetrahydrofuran and dioxane). Toluene is the most preferable in consideration of the solubility of the raw material.

A preferred reaction temperature in the hydrosilylation reaction is below the boiling point of the solvent used. Since the compound to be reacted with the raw material has an unsaturated bond at its terminal, it may spontaneously polymerize during the hydrosilylation reaction. To prevent this, the preferred reaction temperature is 20-80°C. For the purpose of suppressing the polymerization reaction of the (meth)acryloyl group, a polymerization inhibitor such as a phenol derivative, a phenothiazine derivative, an N-nitrosophenylamine salt derivative may be used. The most preferred polymerization inhibitor is hydroquinone monomethyl ether. The preferable amount of use is 1 to 20000 ppm based on the total mass of the reaction solution. A more preferable range of the amount used is 100 to 10000 ppm.

In Scheme (I), known hydrosilylation catalysts can be used without any limitation. For example, platinum-based, palladium-based and rhodium-based catalysts are preferably used.

Examples of such suitable catalysts include, for platinum-based catalysts, chloroplatinic acid, chloroplatinic acid and alcohol complexes, platinum and olefin complexes, platinum and ketone complexes, platinum and vinylsiloxane complexes, colloidal platinum, Examples include a complex of colloidal platinum and vinyl siloxane, and examples of palladium-based catalysts include palladium, a mixture of palladium black and triphenylphosphine, and examples of rhodium-based catalysts include rhodium and rhodium compounds. Among them, a complex of platinum and 1,1,3,3-tetramethyldivinyldisiloxane is most preferred.

Next, usage modes of the polymerizable monomer of the present invention will be described. The polymerizable monomer of the present invention can be suitably used as a component of a dental composition, and the dental composition containing the polymerizable monomer of the present invention can be used as a dental material, specifically a dental composite resin. (Composite resin for caries cavity filling, Composite resin for abutment construction, Composite resin for dental crown), Resin for denture base, Relining material for denture base, Impression material, Luting material (Resin cement, Resin-added glass ionomer cement) ), dental adhesives (orthodontic adhesives, cavity coating adhesives), tooth fissure sealing materials, resin blocks for CAD/CAM, temporary crowns, artificial tooth materials, and the like.

The dental composition containing the polymerizable monomer of the present invention is characterized by high strength of the cured product and small polymerization shrinkage during polymerization and curing. Although the reason why the dental composition containing the polymerizable monomer of the present invention exhibits the above-mentioned excellent effects is not necessarily clear, it is brought about by the bulky hydrocarbon groups represented by R ¹ and R ² . It is presumed that this is due to the rigid monomer molecular skeleton that is That is, the strong polymer network of the polymerizable monomer of the present invention contributes to the development of the strength of the cured product of the dental composition, and the bulky and rigid molecular structure of the polymerizable monomer of the present invention contributes to the strength of the dental composition. It is presumed that lowering the density of reactive groups in the composition for curing contributes to the reduction of polymerization shrinkage during curing. In addition, the dental composition containing the polymerizable monomer of the present invention reduces the risk of delamination between the dental composition and the dentin when heat history is applied, that is, it has excellent marginal sealing properties. Although the reason why the dental composition containing the polymerizable monomer of the present invention exhibits the above-described excellent effects is not necessarily clear, the dental composition containing the polymerizable monomer of the present invention can be compared. Due to its low viscosity, it easily fits into cavities formed in tooth structure, and furthermore, due to the contribution of atomic groups such as silicon constituting the main chain skeleton of the polymerizable monomer of the present invention, the coefficient of thermal expansion is kept low. It is presumed that the small difference in thermal expansion coefficient between the dental composition and the tooth substance contributes to this.

From the above point of view, the thermal expansion coefficient of the dental composition of the polymerizable monomer of the present invention is preferably 5×10 ⁻⁶ to 50×10 ⁻⁶ K, preferably 5×10 ⁻⁶ to 40×10 −6 K. It is more preferably 10 ^-6 K, even more preferably 5×10 ^-6 to 30×10 ^-6 K. By satisfying the above range, the coefficient of thermal expansion is close to that of natural teeth, resulting in excellent marginal sealing properties.

The polymerizable monomer of the present invention is one of the most preferred forms of use in a dental composition together with a polymerization initiator and a filler, and such a dental composition is suitably used as a dental composite resin. .

The polymerization initiator can be selected from polymerization initiators used in general industry, and among them, polymerization initiators used in dental applications are preferably used. In particular, photopolymerization initiators and chemical polymerization initiators are preferably used. One polymerization initiator may be used alone, or two or more polymerization initiators may be used in appropriate combination.

Photopolymerization initiators include (bis)acylphosphine oxides, ketals, α-diketones, coumarins and the like.

Among (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 salts thereof (sodium salts, potassium salts, ammonium salts, etc.) and the like. Bisacylphosphine oxides include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro benzoyl)-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, ( 2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) and the like.

Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

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

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

Examples of 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-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'-ka Rubonyl-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]quinolizin-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. and compounds described in JP-A-10-245525.

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

Among the photopolymerization initiators, by using at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins, photocurability in the visible and near-ultraviolet regions is improved. It is possible to obtain a dental composition which is excellent and shows sufficient photocurability even when using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

Organic peroxides are preferably used as chemical polymerization initiators. The organic peroxide used as the chemical polymerization initiator is not particularly limited, and known ones can be used. Representative organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates, and the like.

Ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide and the like.

Hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like. be done.

Diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like.

Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t- butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne and the like.

Peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy) butane, 2,2-bis(t-butylperoxy)octane, 4,4-bis(t-butylperoxy)valeric acid-n-butyl ester and the like.

Peroxyesters include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t- amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3 ,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleic acid and the like.

Peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate and di-n-propylperoxydicarbonate. , di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate and the like.

Among the organic peroxides, diacyl peroxide is preferably used from the viewpoint of overall balance of safety, storage stability and radical generating ability, and among these, benzoyl peroxide is particularly preferably used.

The content of the polymerization initiator in the dental composition of the present invention is not particularly limited. 0.001 to 30 parts by mass of the polymerization initiator is preferable. If the content of the polymerization initiator is less than 0.001 part by mass with respect to 100 parts by mass, the polymerization may not proceed sufficiently, resulting in a decrease in adhesive strength. The content of the polymerization initiator is more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more based on 100 parts by mass, from the viewpoint of better curability. On the other hand, if the content of the polymerization initiator exceeds 30 parts by mass with respect to the above 100 parts by mass, it may cause precipitation from the dental composition. The content of the polymerization initiator is more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and most preferably 10 parts by mass or less, in order to prevent precipitation from the dental composition.

When the dental composition containing the polymerizable monomer of the present invention is used to produce a dental composite resin, it is preferable that the dental composition further contains a filler. Such fillers are roughly classified into inorganic fillers, organic fillers and organic-inorganic composite fillers.

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, etc., and these may be used alone or It can be used as a mixture of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. The average particle size of the organic filler is preferably from 0.001 to 50 μm, more preferably from 0.001 to 10 μm, from the viewpoint of handleability and mechanical strength of the resulting composition.

Examples of inorganic fillers include various types of glass [containing silica as a main component and, if necessary, oxides such as heavy metals, boron and aluminum. For example, glass powder of general composition such as fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (Pyrex (registered trademark) glass); E-2000, E-3000, manufactured by ESSTECH), strontium borosilicate glass (E-4000, manufactured by ESSTECH), lanthanum glass ceramics (GM31684, manufactured by Schott), fluoroaluminosilicate glass (GM35429, G018-091, G018-117, manufactured by Schott)], various ceramics, composite oxides such as silica-titania, silica-zirconia, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, etc., and these may be used singly or in combination of two or more. They may be used together. Among them, those containing silica as a main component (containing 5% by mass or more, preferably 10% by mass or more) are suitable.

The shape of the inorganic filler is not particularly limited, and it can be used as a powder of amorphous or spherical particles. When an amorphous inorganic filler is used, the mechanical strength and abrasion resistance are particularly excellent, and when a spherical inorganic filler is used, the polishing lubricity and lubricity durability are particularly excellent. The shape of the inorganic filler may be appropriately selected according to the purpose of the dental composition.

The average particle size of the inorganic filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. In this specification, the method for measuring the average particle size of the filler is to disperse the filler in a dispersion medium consisting of at least one selected from alcohol and water, and use laser diffraction particles such as SALD-2300 manufactured by Shimadzu Corporation. It is the median value of the volume particle size distribution when measured with a size distribution measuring device. If the average particle size of the filler is small and falls below the lower limit of measurement in the laser diffraction particle size distribution analyzer, an electron microscope, for example SU3500 or SU9000 manufactured by Hitachi, Ltd., is used to take electron micrographs and randomly select them. The average value of the particle diameters of the 20 particles obtained. When the particles are non-spherical, the particle diameter is the arithmetic mean of the longest and shortest lengths of the particles.

Moreover, in the present invention, the inorganic filler may be in the form of aggregated particles formed by aggregation of the inorganic filler. 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 with an ultrasonic intensity of 40 W 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 agglomerated particles in the present invention include strongly agglomerated particles that are hardly dispersed even under such conditions.

As a method for producing agglomerated particles in which the particles are strongly agglomerated from commercially available inorganic filler agglomerated particles, in order to further increase cohesive force, the inorganic filler is heated to a temperature just before it melts, and the inorganic filler in contact is A method of heating to such an extent that the filler particles are slightly fused together is preferably used. Further, in this case, in order to control the shape of the aggregated particles, an aggregated form may be formed before heating. Examples of such a method include a method in which the inorganic filler is placed in a suitable container and pressurized, or 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.

Furthermore, as another suitable method for producing aggregated particles in which inorganic filler particles are strongly aggregated, silica sol, alumina sol, titania sol, zirconia sol, etc. produced by a wet method are used, and freeze-drying, spray-drying, etc. Aggregated particles in which the particles are strongly aggregated can be easily obtained by drying by the method of (1) and heat-treating as necessary. Specific examples of the sol include Nippon Shokubai Co., Ltd., trade name: Seahoster; JGC Catalysts and Chemicals Co., Ltd., trade name: OSCAL, QUEEN TITANIC; Nissan Chemical Industries, Ltd., trade name: SNOWTEX, Aluminasol, CELNAX. , nano-use, and the like. The shape of the inorganic filler particles is not particularly limited, and can be appropriately selected and used.

Since the inorganic filler is used in a dental composition in combination with a polymerizable monomer, the affinity between the inorganic filler and the polymerizable monomer can be improved, or the inorganic filler and the polymerizable monomer can be improved. In order to increase the chemical bonding with the body and improve the mechanical strength of the cured product, it is desirable to apply a surface treatment in advance with a surface treatment agent. The method of surface treatment is not at all restrictive. Also, known surface treatment agents can be used, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 11 -methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like. The concentration of the surface treatment agent is usually in the range of 0.1-30% by mass, preferably in the range of 1-20% by mass, based on the filler.

The average particle size of the organic-inorganic composite filler is preferably 1-50 μm, more preferably 3-25 μm. If the average particle size of the organic-inorganic composite filler is too small, the stickiness of the dental composition may increase and the operability may deteriorate. If the average particle size is too large, the paste will become rough and dry, resulting in poor operability. In the present invention, the organic-inorganic composite filler indicates a filler containing an inorganic filler and a polymer of polymerizable monomers.

As the organic-inorganic composite filler in the present invention, an inorganic filler having an average particle size of 0.5 μm or less is preferably dispersed in an organic matrix, but the production method is not particularly limited. For example, a known polymerizable monomer described later and a known polymerization initiator described above are added in advance to the inorganic filler, made into a paste, and then polymerized by solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization. , may be prepared by pulverization.

In the dental composition of the present invention, in addition to the polymerizable monomer of the present invention, known polymerizable monomers can be used in combination as needed.

Specific examples of such known polymerizable monomers include α-cyanoacrylic acid, (meth)acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid. Esters such as (meth)acrylamide, (meth)acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives, etc. Among them, (meth) acrylic acid ester and / or (meth) Acrylamide derivatives are preferred.

Examples of the (meth)acrylic acid ester and (meth)acrylamide derivatives are shown below.

(I) monofunctional monomer Monofunctional monomers include, for example, methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2-(N, N -dimethylamino)ethyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 2-hydroxyethyl (meth)acrylate, 3 - hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, (Meth)acrylate polymerizable monomers such as erythritol mono(meth)acrylate, isobornyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide , N,N-(dihydroxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N- (Meth)acrylamide-based polymerizable monomers such as ethyl-N-methyl(meth)acrylamide; (meth)acryloylmorpholine, (meth)acryloyloxide decylpyridinium bromide, (meth)acryloyloxidedecylpyridinium chloride, (meth)acryloyl oxidodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride and the like.

(II) Bifunctional Monomer Examples of the bifunctional monomer include aromatic compound-based bifunctional polymerizable monomers and aliphatic compound-based bifunctional polymerizable monomers.

Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy- 2-hydroxypropoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of added moles of ethoxy group: 1 to 5), 2,2-bis(4-( meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxy Diethoxyphenyl)-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 them, 2,2-bis[4-methacryloyloxypolyethoxyphenyl]propane (average number of added moles of ethoxy group: 2.6), 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl ] propane is preferred.

Examples of aliphatic compound-based bifunctional polymerizable 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, 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-hydroxypropyloxy)ethane, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate and the like. Among them, triethylene glycol dimethacrylate, 1,10-decanediol dimethacrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyl Oxyethyl) dimethacrylate is preferred.

(III) Tri- or higher-functional monomer Examples of tri- or higher-functional monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolmethane tri(meth)acrylate. , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2 ,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4 -oxaheptane and the like.

Each of the above known polymerizable monomers may be used alone or in combination of two or more. Oligomers, prepolymers and polymers obtained by polymerizing the above known polymerizable monomers alone or by copolymerizing two or more of them may be blended into the dental composition of the present invention, if necessary. good.

In addition, in order to improve the adhesiveness to dentin, metals, ceramics, etc., it may be preferable to incorporate a functional monomer that imparts adhesiveness to these adherends into the dental composition of the present invention. .

Examples of the functional monomer include 2-(meth)acryloyloxyethyl dihydrogen phosphate and 10-(meth)acryloyloxydecyl dihydrogen phosphate, since they exhibit excellent adhesion to tooth substance and base metals. , 2-(meth)acryloyloxyethylphenylhydrogenphosphate and other monomers having a phosphoric acid group; and 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid A monomer having a carboxylic acid group such as is preferred.

Further, as the functional monomer, for example, 10-mercaptodecyl (meth) acrylate, 6-(4-vinylbenzyl-n-propyl) amino-1,3 ,5-triazine-2,4-dithione, thiouracil derivatives described in JP-A-10-1473, and compounds containing a sulfur element described in JP-A-11-92461 are preferred.

Further, as the functional monomer, a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane is preferable because it is effective for adhesion to ceramics, porcelain, and other dental compositions.

The dental composition of the present invention contains additives such as a polymerization accelerator, a polymerization inhibitor, an ultraviolet absorber, a fluorescent agent, and a pigment, in addition to the polymerizable monomer, polymerization initiator, and filler described above. It may be contained within a range that does not inhibit the effect of.

Polymerization accelerators include amines, sulfinic acid and its salts, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogensulfites, thiourea. compound and the like.

Amines are divided into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; 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 them, tertiary aliphatic amines are preferred from the viewpoint of curability and storage stability of the dental composition, and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

Examples of aromatic amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis (2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N, N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl)- 3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N- Dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino) Methyl benzoate, 4-(N,N-dimethylamino) 2-butoxyethyl benzoate, 4-(N,N-dimethylamino) 2-(methacryloyloxy) benzoate, 4-(N,N-dimethylamino) ) benzophenone, 4-(N,N-dimethylamino)butyl benzoate, and the like. Among them, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethylamino)ethyl benzoate, 4-( At least one selected from the group consisting of 2-butoxyethyl N,N-dimethylamino)benzoate and 4-(N,N-dimethylamino)benzophenone is preferably used.

Examples of sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and benzenesulphine. sodium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulphine potassium phosphate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate potassium, 2,4,6-triethylbenzenesulfinate lithium, 2,4,6-triethylbenzenesulfinate calcium, 2,4,6-triisopropylbenzenesulfinate, 2, sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. and particularly preferred are sodium benzenesulfinate, sodium p-toluenesulfinate and sodium 2,4,6-triisopropylbenzenesulfinate.

Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethylbarbituric acid. acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5-n- butyl barbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexyl barbituric acid, 1,3-dimethyl- 5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1- Cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid turic acid and thiobarbituric acid, and salts thereof (especially alkali metals or alkaline earth metals are preferred); sodium 3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate;

Particularly preferred barbituric acid derivatives include 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and sodium salts of these barbiturates.

Triazine compounds include, for example, 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis( trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p- methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4 ,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s- triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-[ 2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s -triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6 -bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl )-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis( 2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloro methyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl) -s-triazine, 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine and the like.

Among the triazine compounds exemplified above, particularly preferred ones are 2,4,6-tris(trichloromethyl)-s-triazine from the viewpoint of polymerization activity, and 2-phenyl-4-triazine from the viewpoint of storage stability. ,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-biphenylyl)-4,6-bis( trichloromethyl)-s-triazine. The above triazine compounds may be used alone or in combination of two or more.

As the copper compound, for example, copper acetylacetone, copper (II) acetate, copper oleate, copper (II) chloride, copper (II) bromide, etc. are preferably used.

Examples of tin compounds include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Particularly preferred tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

The vanadium compounds are preferably IV- and/or V-valent vanadium compounds. IV-valent and/or V-valent vanadium compounds include, for example, divanadium tetroxide (IV), vanadium oxide 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), ammonium metavanadate (V), etc. Examples include compounds described in JP-A-96122.

As the halogen compound, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used.

Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among them, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid and the like.

Sulfites include, for example, sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

Hydrogen sulfites include, for example, sodium hydrogen sulfite and potassium hydrogen sulfite.

Thiourea compounds include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di -n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like.

The content of the polymerization accelerator in the dental composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited. It is preferably 0.001 to 30 parts by mass with respect to the total amount of 100 parts by mass. If the content of the polymerization accelerator is less than 0.001 parts by mass, the polymerization may not proceed sufficiently, resulting in a decrease in adhesive strength. The content of the polymerization accelerator is more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more based on 100 parts by mass, from the viewpoint of better curability. On the other hand, if the content of the polymerization accelerator exceeds 30 parts by mass with respect to the above 100 parts by mass, it may cause precipitation from the dental composition. The content of the polymerization accelerator is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less based on the 100 parts by mass, since there is no risk of precipitation from the dental composition.

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. , these may be blended alone or in combination of two or more.

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

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. The test methods, materials, etc. used in the examples are summarized below.

(Nuclear magnetic resonance (NMR) spectrum)
¹ H-NMR spectra were measured at 270 MHz and 400 MHz using JNM-GSX270 spectrometer manufactured by JEOL Ltd. or ULTRA SHIELD 400 PLUS manufactured by Bruker, respectively. Deuterated chloroform was used as a solvent, and tetramethylsilane (TMS) was added as an internal standard.

(Analysis of purity by UPLC)
Apparatus: ACQUITY UPLC (manufactured by Nippon Waters Co., Ltd.)
Column: ACQUITY UPLC BEH C18 1.7 μm (manufactured by Nippon Waters Co., Ltd.)
Mobile phase: methanol/water = 45/55
Flow rate: 0.5mL/min
Detector: RI, UV
Column temperature: 50°C
Injection volume: 1.0 μL

(Gas Chromatography (GC))
Apparatus: GC-2014 (manufactured by Shimadzu Corporation)
Column: DB-1ms (manufactured by Agilent Technologies)
Carrier gas: Nitrogen Detector: FID
Detector temperature: 300°C
Column temperature: After holding at 50°C for 5 minutes, the temperature was raised to 250°C at a heating rate of 20°C/min, then raised to 300°C at a heating rate of 10°C/min, and held at 300°C for 10 minutes. Injection volume: 0.2 μL

(Viscosity of polymerizable monomer)
Viscometer (manufactured by Toki Sangyo Co., Ltd., TV-30E viscometer, JIS K-7117-2: compliant with 1999, cone plate type) using a cone rotor of 0.8 ° × R24, sample amount 0.6 mL, measured at 25°C. After preheating for 1 minute, the measurement was started, and the measured value after 5 minutes was taken as the viscosity.

(Bending strength of cured product)
After vacuum defoaming, the dental composition obtained in each example and comparative example was filled in a stainless steel mold (dimensions 2 mm × 2 mm × 25 mm), pressed against a slide glass on the top and bottom, and irradiated with dental LED light. A test piece of a cured product was obtained by irradiating both sides of the slide glass with light for 10 seconds at 1 point and 5 points on each side with a device (manufactured by Morita Co., Ltd., trade name "Pencure 2000"). Five cured products were produced for each of the examples and comparative examples, and the cured products were stored in distilled water at 37° C. for 24 hours after being removed from the mold. For each test piece, in accordance with JIS T6514: 2015 and ISO4049: 2009, using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name "AGI-100"), the distance between fulcrums is 20 mm, and the crosshead speed is 1 mm. The bending strength was measured by a 3-point bending test under the condition of /min. The bending strength was obtained by calculating the average value of the measured values of each test piece. The bending strength is preferably 100 MPa or more, more preferably 110 MPa or more, and most preferably 120 MPa or more.

(Paste consistency)
0.5 cc of the dental composition paste obtained in each of Examples and Comparative Examples was weighed out, and a load of 1 kg was applied thereon for 30 seconds via a glass plate to crush the paste. Two points, the maximum diameter and the minimum diameter, of the spread disk-shaped paste were measured, and the average value (mm) of the two points was defined as the consistency. The higher the consistency, the softer the paste, and from the viewpoint of paste operability, the thickness is preferably 10 mm or more, more preferably 12 mm or more, and even more preferably 14 mm or more.

(Polymerization shrinkage stress)
The paste (dental composition ) was filled. The glass plate used was sandblasted with alumina powder having a particle size of 50 μm. A stainless steel jig (φ5 mm) connected to a universal testing machine (Autograph AG-100kNI, manufactured by Shimadzu Corporation) was placed on the filled paste. Next, using a dental LED light irradiator (manufactured by Morita Co., Ltd., trade name "Pencure 2000"), the paste was irradiated with light for 20 seconds through a glass plate to cure the paste. At this time, the polymerization shrinkage stress associated with the polymerization (hardening) of the dental composition progressed by the light irradiation was measured with the universal testing machine. The smaller the polymerization shrinkage stress, the smaller the risk of peeling due to shrinkage, and the more the curable composition can be filled at once, improving the operability. The polymerization shrinkage stress is preferably 12 MPa or less, more preferably less than 10 MPa.

(marginal sealing property)
Using a dental air turbine, a cavity with a diameter of about 4 mm and a depth of about 3 mm is formed in the extracted bovine tooth, and a photopolymerization type dental bonding material (manufactured by Kuraray Noritake Dental Co., Ltd., trade name: After applying “Clearfill (registered trademark) Universal Bond Quick”), light was irradiated for 10 seconds with a dental LED light irradiation device (manufactured by Morita Co., Ltd., trade name “Pencure 2000”). The bonding material was cured. Next, after filling the cavity with the dental composition paste obtained in each of Examples and Comparative Examples, the filled dental composition was cured by light irradiation for 20 seconds using the dental light irradiator. let me Next, in order to prevent the penetration of the dye from the root apex and the crown fissure, a photopolymerization type dental bonding material (manufactured by Kuraray Noritake Dental Co., Ltd., trade name “Clearfill (registered trademark) Megabond (registered trademark)” ”) was applied to a portion other than the cavity restoration portion and its peripheral portion, and cured by light irradiation for 30 seconds with the above dental light irradiator to obtain a test piece. Five test pieces were produced. Next, the test piece was left in a thermostat set at 37° C. for 24 hours while being immersed in distilled water in the sample container. After taking out the test piece and alternately immersing it in cold water (distilled water) at 4°C and hot water (distilled water) at 60°C for 1 minute each, 2500 heat cycles were performed, followed by 0.2% basic fuchsin aqueous solution at 37°C. for 24 hours, washed with water, and dried with a dental air syringe. After drying, the specimens were divided into three by cutting the repaired portion lengthwise with a low speed diamond cutter to make 3 sections from 1 specimen, ie 15 sections from 5 specimens. Then, for these 15 sections, the penetration of the dye into the enamel cavity edge and the dentin cavity edge was observed under an optical microscope, and each site was scored according to the following criteria. The average score for the sections was calculated. This average value is preferably 1.5 or less, more preferably 1.0 or less, in order to reduce the risk of detachment between the dental composition and the dentin when heat history is applied to the dental composition. .
Score 0: No penetration of pigment into both cavity wall and cavity bottom.
Score 1: No dye invasion is observed in the cavity bottom, but less than 1/2 of the cavity wall is observed in the cavity wall.
Score 2: No pigment invasion was observed in the cavity bottom, but pigment penetration was observed in the cavity wall in an area of 1/2 or more of the cavity wall.
Score 3: Penetration of pigment is observed in both the cavity wall and the cavity bottom.

[Example 1]
(Synthesis of diphenylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as DPPS))
Allyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., 12.6 g, 100 mmol) was weighed in a 100 mL eggplant flask, and p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd., 100 mg) was added and stirred. Two drops of platinum-divinyltetramethyldisiloxane complex (manufactured by Gelest Co., Ltd.) as a catalyst were added into the system using a dropper, and diphenylsilane (manufactured by Gelest Co., 7.37 g, 40 mmol) was added. After that, the mixture was reacted for 7 days with stirring at room temperature. After reacting for 7 days, a portion of the reaction solution was sampled and subjected to ¹ H-NMR measurement to confirm the progress of the reaction. As a result, disappearance of the H—Si—H peak derived from the starting material was confirmed, and the reaction was terminated. The resulting yellow liquid was purified using silica gel column chromatography (solvent: n-hexane/ethyl acetate = 30/1 (volume ratio)), and the solvent was distilled off under reduced pressure using a rotary evaporator. , a clear and colorless liquid was obtained. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the obtained transparent and colorless liquid was the intended polymerizable monomer (DPPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 320 cP.

[Example 2]
(Synthesis of methylphenylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as MPPS))
Synthesis was carried out in the same manner as in Example 1, except that methylphenylsilane (manufactured by Gelest, 4.88 g, 40 mmol) was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the obtained transparent and colorless liquid was the intended polymerizable monomer (MPPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 36 cP.

[Example 3]
(Synthesis of methylphenylbis[3-(methacryloxy)undecyl]silane (hereinafter referred to as MPUS))
In Example 1, allyl methacrylate was changed to 10-undecenyl methacrylate synthesized by the method described in Example 1 of JP-A-63-211252, and diphenylsilane was replaced with methylphenylsilane (2.45 g, 20 mmol ) and 10-undecenyl methacrylate (10.72 g, 45 mmol). Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the resulting colorless transparent liquid was the intended polymerizable monomer (MPUS represented by the following formula). The resulting polymerizable monomer had a viscosity of 71 cP.

[Synthesis Example 1]
(Synthesis of dicyclohexylsilane)
9.55 g (0.036 mol) of dicyclohexyldichlorosilane (manufactured by Gelest) and 90 mL of toluene were placed in a 300 mL two-necked flask equipped with a thermometer, condenser, dropping funnel and stirring device. The solution in the flask was stirred while being maintained at 0° C. or lower, and 21 mL of a toluene solution of sodium bis(2-methoxyethoxy)aluminum hydride (concentration: about 3.6 mol/L) was slowly added dropwise from the dropping funnel. After completion of the dropwise addition, the temperature was gradually raised to room temperature, and the mixture was stirred for 4 hours to carry out a reduction reaction. During this period, the raw materials and products were dissolved in the reaction solution, and the reaction system was homogeneous. Thereafter, the reaction mixture was hydrolyzed, extracted with cyclopentyl methyl ether, and the extract was concentrated under reduced pressure to obtain a colorless liquid. The resulting colorless liquid was analyzed by gas chromatography (GC) and ¹ H-NMR, confirming the formation of dicyclohexylsilane. Further, when an internal standard substance was added at the time of ¹ H-NMR measurement and the reaction yield was calculated, the yield of dicyclohexylsilane was 75%.

[Example 4]
(Synthesis of dicyclohexylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as DCyhPS))
Synthesis was carried out in the same manner as in Example 1, except that dicyclohexylsilane (7.78 g, 40 mmol) obtained in Synthesis Example 1 was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the resulting colorless transparent liquid was the intended polymerizable monomer (DCyhPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 270 cP.

[Synthesis Example 2]
(Synthesis of cyclohexylmethylsilane)
Synthesis was carried out in the same manner as in Synthesis Example 1, except that cyclohexylmethyldichlorosilane (manufactured by Gelest, 7.1 g, 0.036 mmol) was used instead of dicyclohexyldichlorosilane. The resulting colorless liquid was analyzed by gas chromatography (GC) and ¹ H-NMR, confirming the formation of cyclohexylmethylsilane. Further, when an internal standard substance was added at the time of ¹ H-NMR measurement and the reaction yield was calculated, the yield of cyclohexylmethylsilane was 86%.

[Example 5]
(Synthesis of cyclohexylmethylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as CyhMPS))
Synthesis was carried out in the same manner as in Example 1, except that cyclohexylmethylsilane (5.13 g, 40 mmol) obtained in Synthesis Example 2 was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the resulting colorless transparent liquid was the desired polymerizable monomer (CyhMPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 9 cP.

[Synthesis Example 3]
(Synthesis of dicyclopentylsilane)
Synthesis was carried out in the same manner as in Synthesis Example 1, except that dicyclopentyldichlorosilane (manufactured by Gelest, 8.54 g, 0.036 mmol) was used instead of dicyclohexyldichlorosilane. The resulting colorless liquid was analyzed by gas chromatography (GC) and ¹ H-NMR, confirming the formation of dicyclopentylsilane. Further, when an internal standard substance was added at the time of ¹ H-NMR measurement and the reaction yield was calculated, the yield of dicyclopentylsilane was 71%.

[Example 6]
(Synthesis of dicyclopentylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as DCypPS))
Synthesis was carried out in the same manner as in Example 1, except that dicyclopentylsilane (6.73 g, 40 mmol) obtained in Synthesis Example 3 was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the obtained transparent and colorless liquid was the intended polymerizable monomer (DCypPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 90 cP.

[Synthesis Example 4]
(Synthesis of di-tert-butylsilane)
Synthesis was carried out in the same manner as in Synthesis Example 1, except that di-t-butyldichlorosilane (manufactured by Gelest, 7.68 g, 0.036 mmol) was used instead of dicyclohexyldichlorosilane. The resulting colorless liquid was analyzed by gas chromatography (GC) and ¹ H-NMR, confirming the formation of di-tert-butylsilane. Further, when an internal standard substance was added at the time of ¹ H-NMR measurement and the reaction yield was calculated, the yield of di-tert-butylsilane was 71%.

[Example 7]
(Synthesis of di-tert-butylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as DtBPS))
Synthesis was carried out in the same manner as in Example 1, except that di-tert-butylsilane (5.77 g, 40 mmol) obtained in Synthesis Example 4 was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the obtained transparent and colorless liquid was the intended polymerizable monomer (DtBPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 4 cP.

[Example 8]
(Synthesis of 1-adamantylmethylbis[3-(methacryloxy)propyl]silane (hereinafter referred to as AMPS))
Synthesis was carried out in the same manner as in Example 1, except that 1-adamantylmethylsilane (manufactured by Capot Chemical Co., 7.21 g, 40 mmol) was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the obtained transparent and colorless liquid was the intended polymerizable monomer (AMPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 550 cP.

[Example 9]
(Synthesis of dimorpholino-[3-(methacryloxy)propyl]silane (hereinafter referred to as DMoPS))
Synthesis was carried out in the same manner as in Example 1, except that bismorpholinosilane (manufactured by Gelest, 8.09 g, 40 mmol) was used instead of diphenylsilane. Purification yielded a colorless and transparent liquid. From ¹ H-NMR measurement and UPLC analysis, it was confirmed that the resulting colorless transparent liquid was the desired polymerizable monomer (DMoPS represented by the following formula). The resulting polymerizable monomer had a viscosity of 870 cP.

[Examples 10-22 and Comparative Examples 1-2]
Each paste (dental composition) was prepared by mixing the polymerizable monomers of Examples 1 to 9 and the raw materials shown below in the mass ratio shown in Table 1 at normal temperature (23 ° C.) in a dark place. did. Each characteristic of these pastes was examined by the method described above.

(Polymerizable monomer)
3G: triethylene glycol dimethacrylate DD: 1,10-decanediol dimethacrylate D2.6E: 2,2-bis[4-methacryloyloxypolyethoxyphenyl]propane (average number of added moles of ethoxy groups: 2.6)
UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate Bis-GMA: 2,2-bis[4-[3-methacryloyloxy-2-hydroxypropoxy]phenyl]propane

(Photoinitiator)
CQ: camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

(Polymerization accelerator)
PDE: 4-(N,N-dimethylamino)ethyl benzoate

(Polymerization inhibitor)
BHT: 3,5-di-t-butyl-4-hydroxytoluene

(Inorganic filler)
UF1.0: 3-methacryloyloxypropyltrimethoxysilane surface-treated barium glass powder, “GM27884 UF1.0” manufactured by Schott, average particle size 1.0 μm
NF180: 3-methacryloyloxypropyltrimethoxysilane surface-treated barium glass powder, “GM27884 NF180” manufactured by Schott, average particle size 0.18 μm
P-500: Produced according to Production Example 1 described later.

(Organic-inorganic composite filler)
An organic-inorganic composite filler (CF) was produced according to Production Example 2 described later.

[Production Example 1]
Aggregated silica “Silica Microbead P-500 (average primary particle diameter 12 nm, aggregate average particle diameter 2 μm)” (manufactured by Nikki Shokubai Kasei Co., Ltd.) 100 g, 3-methacryloxypropyltrimethoxysilane 20 g, and toluene 200 mL was placed in a three-necked flask and stirred at room temperature for 2 hours. After toluene was distilled off under reduced pressure, vacuum drying was performed at 40° C. for 16 ^hours , followed by heating at 90° C. for 3 hours. An inorganic filler (P-500) with a pore volume of 0.19 mL/g was obtained.

[Production Example 2]
1% by mass of azobisisobutyronitrile (AIBN) was previously dissolved as a polymerization initiator, and 100 parts by mass of a polymerizable monomer mixture of Bis-GMA and 3G (mass ratio 1:1) was added as an inorganic filler. 100 parts by mass of NF180 was added and mixed to form a paste. This was polymerized by heating at 100° C. under reduced pressure for 5 hours. The resulting polymerized and cured product was pulverized using a vibrating ball mill until the average particle size reached 5 μm. 100 g of the pulverized filler thus obtained was subjected to surface treatment by refluxing in 200 mL of an ethanol solution containing 2% by mass of γ-methacryloyloxypropyltrimethoxysilane at 90° C. for 5 hours to obtain an organic-inorganic composite filler (CF). rice field.

As shown in Table 1, the dental composition containing the polymerizable monomer of the present invention has higher flexural strength, lower polymerization shrinkage stress, and a preferred range of consistency compared to the comparative examples. The result was that it was superior to

The polymerizable monomer of the present invention can be suitably used for dental compositions, particularly dental composite resins.

Claims (10)

General formula (1) below

{wherein R ¹ and R ² are each independently an optionally substituted C 1-20 aliphatic saturated hydrocarbon group, an optionally substituted C 3-20 An alicyclic hydrocarbon group, a polycyclic hydrocarbon group which is a group selected from the group consisting of the following general formulas (a-1) to (a-8) which may have a substituent, a substituent an aryl group having 6 to 20 carbon atoms which may have, or a morpholino group,
the substituent is an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms substituted with a halogen atom;

R ³ and R ⁴ are each independently a divalent saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and the substituent is an alkyl group having 1 to 5 carbon atoms. , a halogen atom (excluding a fluorine atom) or a halogenated alkyl group having 1 to 5 carbon atoms substituted with a halogen atom,
X ¹ and X ² are each independently a (meth)acryloxy group or a (meth)acrylamide group,
excluding diphenylbis[3-((meth)acryloxy)propyl]silane in general formula (1)}
A polymerizable monomer represented by 2. The polymerizable monomer according to claim 1, which has a viscosity at 25° C. of 1000 cP or less. each of R ¹ and R ² is independently an optionally substituted monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or 6 to 20 carbon atoms which may be substituted; 3. The polymerizable monomer according to claim 1, which is a monovalent aromatic hydrocarbon group of 4. The polymerizable monomer according to any one of claims 1 to 3, wherein R ¹ and/or R ² is a phenyl group which may have a substituent. At least one of R ¹ and R ² is an unsubstituted phenyl group (with the proviso that both R ¹ and R ² are unsubstituted phenyl groups, and X ¹ and X ² are (meta ) is an acryloxy group and R ³ and R ⁴ are propylene groups), the polymerizable monomer according to claim 4 . The polymerizable unit according to any one of claims 1 to 5, wherein R ³ and R ⁴ are each independently an unsubstituted divalent saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms. Quantity. 7. The polymerizable unit according to any one of claims 1 to 6, wherein R ³ and R ⁴ are each independently an unsubstituted divalent saturated aliphatic hydrocarbon group having 3 to 11 carbon atoms. Quantity. General formula (1) below

{wherein R ¹ and R ² are each independently an optionally substituted C 1-20 aliphatic saturated hydrocarbon group, an optionally substituted C 3-20 An alicyclic hydrocarbon group, a polycyclic hydrocarbon group which is a group selected from the group consisting of the following general formulas (a-1) to (a-8) which may have a substituent, a substituent an aryl group having 6 to 20 carbon atoms which may have, or a morpholino group,
the substituent is an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms substituted with a halogen atom;

R ³ and R ⁴ are each independently a divalent saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and the substituent is an alkyl group having 1 to 5 carbon atoms. , a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms substituted with a halogen atom,
X ¹ and X ² are each independently a (meth)acryloxy group or a (meth)acrylamide group}
A dental composition containing a polymerizable monomer represented by 9. A dental composition according to claim 8, further comprising a polymerization initiator and a filler. A dental composite resin comprising the dental composition according to claim 8 or 9.