JP5143580B2 - Dental composition and composite resin using the same - Google Patents

Description

  The present invention relates to a dental composition used as a dental material, particularly a dental composite resin, having a small polymerization shrinkage upon curing, excellent bending strength of the cured product, and high aesthetics. The present invention also relates to a composite resin having a small polymerization shrinkage upon curing, excellent bending strength of the cured product, and high aesthetics.

  Conventionally, in the field of dental materials, a composition containing a radical polymerizable monomer typified by (meth) acrylic acid ester is typified by a composite resin used for restoration of caries or fracture of natural teeth. It is widely used for dental restoration materials, various dental adhesives used for bonding composite resins and teeth, artificial teeth, denture base materials, and the like.

  In recent years, composite resins have been widely used in place of metal materials that have been used in the past because they have aesthetics close to natural teeth and excellent operability. These composite resins are generally composed mainly of a polymerizable monomer, a polymerization initiator, and a filler. However, as a polymerizable monomer, the in vivo safety, the mechanical strength of a cured product, From the viewpoint of wear resistance, radical polymerizable polyfunctional (meth) acrylates are used. Among them, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly referred to as Bis-GMA) and 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) ) Dimethacrylate (commonly referred to as UDMA) is widely used. In particular, Bis-GMA has been used as a polymerizable monomer for most dental composite resins since Bowen first proposed its application in dental materials in 1962.

  Although dental composite resins have come to be widely used in clinical practice today, improvements are desired in the following respects. In other words, there is still room for improvement in the bending strength, elastic modulus and abrasion resistance of cured products, reduction in water absorption and discoloration, reduction in polymerization shrinkage during curing, transparency and aesthetics similar to natural teeth. It is pointed out that it is big. Particularly in recent years, the polymerization shrinkage causes the generation of a contraction gap that occurs when the dental composite resin is peeled off from the adhesive surface. Therefore, it is strongly desired to reduce the polymerization shrinkage as much as possible. The occurrence of a contraction gap causes secondary caries, pulp stimulation, coloring, and restoration loss. In addition, there is an increasing demand for aesthetics, and dental composite resins often use high refractive index fillers to impart X-ray contrast, so that the composite resin has transparency close to natural teeth. Therefore, it is desired that the polymerizable monomer used has a high refractive index. Further, from the viewpoint of durability (impact resistance and fracture resistance) in the oral cavity, high bending strength is desired.

  On the other hand, in Patent Document 1, a sulfur-containing unsaturated carboxylic acid ester compound represented by the following general formula (3) is used for a dental material in order to improve transparency and reduce polymerization shrinkage. It is disclosed. However, a dental material using the sulfur-containing unsaturated carboxylic acid ester compound has a problem that bending strength is low.

[In the above formula, R ₁₁ represents a divalent organic group, and each X ₁₁ independently represents an oxygen atom, a sulfur atom, a —COO— group or a (CH ₂ ) _q X ₁₂ — group (wherein X ₁₂ represents an oxygen atom or Represents a sulfur atom, q represents an integer of 1 to 3), R ₁₂ each independently represents a hydrogen atom or an alkyl group, and R ₁₃ each independently represents a substituent containing a sulfur atom. And each R ₁₄ independently represents a hydrogen atom or a methyl group. ]

  Patent Document 2 is represented by the following general formula (4) as a polymerizable monomer that gives a polymerized cured product having a high refractive index and high strength and can be suitably used as a matrix monomer for a dental restoration material. A polymerizable unsaturated bond-containing N-substituted amide compound having an amide bond in such a molecular structure is disclosed. And the dental composition which added the filler and the polymerization initiator to this polymeric monomer is also disclosed. However, this dental composition has a problem in polymerization shrinkage characteristics.

  Patent Document 3 discloses a polymerizable monomer of a macromonomer having a (meth) acryl group represented by the following general formula (5) as an agent for improving polymerization shrinkage characteristics, mechanical strength, transparency, and the like. The body is disclosed. In the dental composition containing this polymerizable monomer, the shrinkage of polymerization is reduced by reducing the crosslinking density of the polymerizable monomer, but the bending strength of the cured product is reduced among the mechanical strength. There is a disadvantage that is inevitable.

Wherein each E is independently a hydroxyl group or an ester residue, at least one E is an ester residue, R is a diether-containing residue, etc., and R ₂₁ is hydrogen or 1 to 12 carbons. An alkyl having an atom, R ₂₂ is a bifunctional alkyl having 1 to 12 carbon atoms, and n is an integer of at least 1)

  On the other hand, studies have been made to apply a (meth) acrylate polymerizable monomer having a silicon atom introduced into its molecular structure to a dental composite resin. It is said that by using a polymerizable monomer having a silicon atom introduced into the molecule for a dental composition, it is possible to improve mechanical strength, reduce polymerization shrinkage, and reduce the water absorption of a cured product. .

  For example, Non-Patent Document 1 and Non-Patent Document 2 report a polymerizable monomer represented by the following general formula (6). However, the cured product obtained from the polymerizable composition containing the polymerizable monomer has a low strength, and hardly improved the polymerization shrinkage. Moreover, the refractive index of these polymerizable monomers is low, and when used for a dental composite resin, there is a problem that the transparency thereof becomes extremely low.

  Patent Document 4 and Non-Patent Document 3 disclose application of a polymerizable monomer having a siloxane skeleton as represented by the following general formula (7) to a dental material. However, even when these polymerizable monomers are used as a dental composite resin, the strength of the cured product is at a level lower than that of conventionally used polymerizable monomers. Also, the improvement in polymerization shrinkage is not significant.

International Publication No. 2002/034207 Pamphlet JP 2000-24069A International Publication No. 96/19179 Pamphlet US Pat. No. 5,081,164 J. et al. S. Kuo, et al. "Journal of Dental Research Abstracts", 6A, Abstract No. 30 (1985) Antonucci, J.A. M, et al. , “Polymeric Materials Science and Engineering”, 59, 388-391 (1988). J. et al. H. Lai, et al. , “Dental Materials”, 20, 570-578 (2004).

  An object of the present invention is to provide a dental composition having a small polymerization shrinkage at the time of curing, excellent bending strength of the cured product, and high aesthetics. Another object of the present invention is to provide a dental composite resin having a small polymerization shrinkage at the time of curing, an excellent bending strength of the cured product, and a high aesthetic property.

  The above-mentioned problem is solved by using a polymerizable monomer represented by the following general formula (1) (hereinafter sometimes referred to as polymerizable monomer (1)) as an essential component of a dental composition. The That is, the present invention provides the following general formula (1)

{Wherein R ¹ , R ² , R ³ and R ⁴ represent the following general formula (2)

(Wherein Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms)
Or an alkyl group having 1 to 6 carbon atoms, at least one of which is a group represented by the general formula (2),
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group,
X ¹ and X ² are each independently an oxygen atom, a sulfur atom or NH,
k and l are each independently an integer of 2 to 12, and m and n are each independently an integer of 0 to 4}
It is a dental composition containing the polymerizable monomer represented by these.

At this time, it is preferable that at least one of R ¹ and R ³ and at least one of R ² and R ⁴ are a group represented by the general formula (2), and R ¹ = R ³ and R More preferably, ² = R ⁴ . Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ are preferably hydrogen atoms, X ¹ and X ² are preferably oxygen atoms, and m and n are 0. It is preferable that k and l are each independently an integer of 2 to 6.

  The dental composition of the present invention preferably further contains a polymerization initiator and a filler. The polymerization initiator is preferably a photopolymerization initiator.

  The present invention is also a composite resin using the dental composition described above.

  The polymerizable monomer (1) is characterized in that the cured product has a high bending strength and has a small polymerization shrinkage rate upon polymerization and curing. Therefore, a dental material such as a composite resin using a dental composition containing the polymerizable monomer (1) has excellent durability in the oral cavity, and there is a contraction gap between the dental material and the adhesive surface. It is less likely to occur and concerns such as secondary caries, pulp stimulation, and loss of restorations are reduced. In addition, the polymerizable monomer (1) and the polymer thereof have a high refractive index, and have a refractive index substantially the same as that of dental fillers used in recent years. Therefore, when the dental composition of the present invention containing the polymerizable monomer (1) is applied to a dental material such as a composite resin, it is possible to ensure transparency and to provide a dental material with excellent aesthetics. can do.

  The polymerizable monomer (1) essential contained in the dental composition of the present invention is represented by the above general formula (1), and is a bifunctional compound having two (meth) acryloyl groups as polymerizable groups. Polymerizable monomer. And the greatest feature of the molecular structure is that it has the following molecular structure in an organic group connecting two (meth) acryloyl groups. That is, it is a structure in which two silicon atoms are connected by a siloxane bond and directly substituted by at least one aromatic group (substituted or unsubstituted phenyl group).

  Furthermore, an oxygen atom, a sulfur atom, or NH is bonded to the (meth) acryloyl group, and these are connected to these two silicon atoms via a linear spacer. The spacer has the following molecular structure, and the spacer and the silicon atom are bonded by a Si—C bond.

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are represented by the following general formula (2)

(Wherein Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms)
Or an alkyl group having 1 to 6 carbon atoms, at least one of which is represented by the general formula (2), and R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group. X ¹ and X ² are each independently an oxygen atom, a sulfur atom or NH, k and l are each independently an integer of 2 to 12, and m and n are each independently an integer of 0 to 4. is there.

The halogen atom represented by Y ¹ to Y ⁵ in the general formula (2) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by Y ^{1 to} Y ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group and the like.

  Specific examples of the group represented by the general formula (2) include the following:

{R ^7a , R ^7b , R ^7c , R ^7d , and R ^7e are each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n- A butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, or an n-hexyl group is shown. }

  More specifically, the following are mentioned.

Examples of the alkyl group having 1 to 6 carbon atoms that can be selected from R ^{1 to} R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples include tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group and the like, and it is a methyl group in consideration of the availability of raw materials and steric hindrance during condensation reaction. It is preferable.

  From this viewpoint, the linking group exemplified in the polymerizable monomer (1)

Specific examples of these include the following.

Furthermore, for sufficient bending strength and high refractive index in dental material applications, and further reduction in polymerization shrinkage, at least one of R ¹ and R ³ and at least one of R ² and R ⁴ are represented by the general formula (2). In addition to this, R ¹ = R ³ , R ² = R ⁴ , and as a result, each silicon atom has two aromatic groups (substituted or unsubstituted phenyl). Group) is bonded, that is, it is more preferable that four aromatic groups are introduced into the molecular structure. Examples of the structure exemplified as a particularly suitable linking group from this viewpoint include the following.

Of these, Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ are hydrogen atoms because of the availability of raw materials and the ease of synthesis, that is, a group represented by the general formula (2) More preferred is a phenyl group.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of safety of a group that is eliminated when hydrolysis occurs.

X ¹ and X ² are particularly preferably oxygen atoms.

  In the spacer structure linking the silicon atom and the polymerizable group, m and n are preferably 0 from the viewpoints of availability of raw materials, ease of synthesis, and mechanical properties. Among dental materials, temporary crowns, denture base soft lining materials, impression materials, and the like are required to have high bending strength as mechanical properties, and the elastic modulus is desired not to be higher than necessary. The temporary crown is a material that is temporarily put until a prosthesis such as a crown is put in a cavity in which teeth are shaved, and it is preferable that the elastic modulus is not high in consideration of the ease of removing the temporary crown. Therefore, when the dental composition of the present invention is used for a temporary crown, it is preferable that k and l are each independently an integer of 4 to 12, k and l are 7 to 12, and m and n Is more preferably 0. On the other hand, for applications such as composite resins, denture base resins, CAD / CAM resin blocks, etc., a high elastic modulus is required. From the viewpoint of obtaining a high elastic modulus by applying the polymerizable monomer (1) to a composite resin or the like, it is preferable that k and l are each independently an integer of 2 to 6, and k and l are 3 More preferably, m and n are 0. In this case, both bending strength and elastic modulus are excellent.

  Examples of the polymerizable monomer (1) include the following compounds (wherein, s and t are the same as the definitions of k and l, respectively, u and v are the definitions of m and n, respectively) The same).

  Although the manufacturing method of a polymerizable monomer (1) is not specifically limited, In order to couple | bond an organic group with a silicon atom, the method of synthesize | combining according to the following two schemes is used preferably. That is, one is a method of bonding a (meth) acrylate-like compound having a terminal unsaturated bond to a disiloxane compound (raw material) having a Si—H group as shown in the following scheme (8) by a hydrosilylation reaction. The other is a method of condensing a (meth) acrylate-like compound having a hydrolyzable silyl group as shown in the following scheme (9).

  In Scheme (8), the raw material having a Si—H group can be synthesized by a known method. For example, D.D. Strauss, et al. Am. Chem. Soc. , 112, 2673-2681 (1990), an aromatic chlorosilane can be condensed in acetonitrile to obtain a raw material having a Si—H group.

  Moreover, 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 the raw material can be easily dissolved without reacting with the organic solvent. 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). Considering the solubility of the raw material, toluene is most preferable.

  The preferable reaction temperature in the hydrosilylation reaction is not higher than the boiling point of the solvent used. Since the compound to be reacted with the raw material has an unsaturated bond at the terminal, there is a risk of spontaneous polymerization during the hydrosilylation reaction. In order to prevent this, a preferable reaction temperature is 20 to 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, or an N-nitrosophenylamine salt derivative may be used. The most preferred polymerization inhibitor is hydroquinone monomethyl ether. The preferred amount of use is 1 to 20000 ppm based on the total weight of the reaction solution. A more preferable range of the amount used is 100 to 10,000 ppm.

  In scheme (8), any known hydrosilylation catalyst may be used without any limitation. For example, platinum-based, palladium-based and rhodium-based catalysts are preferably used.

  Examples of such suitable catalysts include platinum-based catalysts such as chloroplatinic acid, chloroplatinic acid and alcohol complexes, platinum and olefin complexes, platinum and ketone complexes, platinum and vinylsiloxane complexes, colloidal platinum, Colloidal platinum and vinyl siloxane complexes, etc. include palladium, palladium black and triphenylphosphine mixtures for palladium catalysts, and rhodium, rhodium compounds for rhodium catalysts. Of these, a complex of platinum and 1,1,3,3-tetramethyldivinyldisiloxane is most preferable.

  In scheme (9), the hydrolyzable group Z that undergoes the condensation reaction is preferably —OH or —Cl. Moreover, when using the (meth) acrylate-like compound whose hydrolyzable group Z is -OH, an acid catalyst is required. As the acid, known ones can be used without any limitation. For example, hydrochloric acid and sulfuric acid are preferably used. Preferred examples of the organic solvent are aliphatic hydrocarbons (eg, hexane and heptane) and aromatic hydrocarbons (eg, toluene and xylene).

  The polymerizable monomer (1) is characterized in that the cured product has a high bending strength and has a small polymerization shrinkage rate upon polymerization and curing. Therefore, the dental composition of the present invention containing the polymerizable monomer (1) is suitable for a dental material, and particularly suitable for a filling restoration composite resin for treating a carious cavity. A dental material such as a composite resin using the dental composition of the present invention has a small polymerization shrinkage at the time of curing, and an excellent bending strength of the cured product, so that it has excellent durability in the oral cavity, and also has an adhesive surface with the dental material. Contrast gaps are unlikely to occur between the two, and concerns such as secondary caries, pulp stimulation, and loss of restorations are reduced. In addition, the polymerizable monomer (1) and the polymer thereof have a high refractive index, and have a refractive index substantially the same as that of dental fillers used in recent years. Therefore, when the dental composition of the present invention containing the polymerizable monomer (1) is applied to a dental material such as a composite resin, it is possible to ensure transparency and to provide a dental material with excellent aesthetics. can do. Furthermore, the polymerizable monomer (1) has a low viscosity as compared with a conventional methacrylate polymerizable monomer having the same molecular weight, and is familiar with the filler blended in the composite resin. Therefore, in the present invention, the filler content of the composite resin can be increased, and a cured product having higher bending strength can be obtained.

  The dental composition of the present invention containing a polymerizable monomer (1) includes a dental composite resin (composite resin for caries cavity filling, composite resin for abutment construction, composite resin for crowns), denture base resin, Denture base lining material, impression material, bonding material (resin cement, resin-added glass ionomer cement), dental adhesive (orthodontic adhesive, adhesive for cavity application), tooth cleft sealant, It can be used as a dental material such as a CAD / CAM resin block, a temporary crown, or an artificial tooth material.

  In particular, a dental composition containing a polymerizable monomer (1), a polymerization initiator, and a filler is one of the most preferred usage forms, and such a dental composition is suitably used as a dental composite resin. It is done.

  As the polymerization initiator, a known polymerization initiator can be used, and is usually selected in consideration of the polymerizability of the polymerizable monomer and the polymerization conditions.

When performing room temperature polymerization, for example, a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined is preferably used. When using a redox polymerization initiator, it is necessary to take a packaging form in which an oxidizing agent and a reducing agent are separately packaged, and to mix them both immediately before use. Examples of the oxidizing agent include organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy- Examples include 2-ethylhexanoate and t-butyl peroxyisopropyl carbonate. Examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane. Examples of ketone peroxides include methyl ethyl ketone peroxide. Examples of the hydroperoxides include t-butyl hydroperoxide. As the reducing agent, a tertiary amine is usually used. For example, 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-i- Propylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N , N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4 − Tylaniline, N, N-bis (2-hydroxyethyl) -4-i-propylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-di (2-hydroxyethyl) ) -3,5-di-i-propylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid n-butoxyethyl, 4-dimethylaminobenzoic acid (2-methacryloyloxy) ethyl, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, ( 2-dimethylamino) ethyl methacrylate, N, N-bis ( Tacryloyloxyethyl) -N-methylamine, N, N-bis (methacryloyloxyethyl) -N-ethylamine, N, N-bis (2-hydroxyethyl) -N-methacryloyloxyethylamine, N, N-bis ( And methacryloyloxyethyl) -N- (2-hydroxyethyl) amine and tris (methacryloyloxyethyl) amine. In addition to these organic peroxide / amine systems, redox systems such as cumene hydroperoxide / thiourea system, ascorbic acid / Cu ²⁺ salt system, organic peroxide / amine / sulfinic acid (or its salt) system, etc. A polymerization initiator can be used. Further, tributylborane, organic sulfinic acid and the like are also preferably used as the polymerization initiator.

  In the case of performing photopolymerization by irradiation with visible light, redox initiators such as α-diketone / tertiary amine, α-diketone / aldehyde, α-diketone / mercaptan are preferable. Examples of the photopolymerization initiator include α-diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent. Examples of α-diketones include camphorquinone, benzyl, 2,3-pentanedione and the like. Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone include 2-chlorothioxanthone and 2,4-diethylthioxanthone. Examples of the reducing agent include Mihira-ketone and the like; 2- (dimethylamino) ethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl N, N-dimethylaminobenzoate, 4-dimethylaminobenzoic acid butyl, 4-dimethylaminobenzoic acid butoxyethyl, N-methyldiethanolamine, 4-dimethylaminobenzophenone, N, N-bis (2-hydroxyethyl) -p-toluidine, dimethylaminophenanthol, etc. Tertiary amines of: aldehydes such as citronellal, lauryl aldehyde, phthaldialdehyde, dimethylaminobenzaldehyde, terephthalaldehyde; 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, 4-mercaptoacetate Enon, it may be mentioned a compound having a thiosalicylic acid, thiol group such as thio benzoic acid. An α-diketone / organic peroxide / reducing agent system obtained by adding an organic peroxide to these redox systems is also preferably used.

  In the case of performing photopolymerization by ultraviolet irradiation, benzoin alkyl ether, benzyl dimethyl ketal and the like are preferable. Furthermore, a photopolymerization initiator of (bis) acylphosphine oxides is also preferably used. Among the (bis) acylphosphine oxides, examples of the acylphosphine oxide include 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- And dimethylphenyl) phosphonate. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and 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- (2,4,4) 6-Trimethylbenzoyl) phenyl Scan fins oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide. These (bis) acylphosphine oxide photopolymerization initiators can be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans, and sulfinates. The above visible light photopolymerization initiator can also be suitably used in combination.

  The said polymerization initiator can be used individually or in combination of 2 or more types, and a compounding quantity is the range of 0.01-20 weight% normally with respect to the whole composition, Preferably 0.1-5 weight% Used in the range of

  When a dental composite resin is produced using the dental composition of the present invention, a filler is further blended. Such fillers are roughly classified into inorganic fillers and organic fillers.

  Examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer, Examples include fillers such as styrene-butadiene copolymers.

  Examples of inorganic fillers include various glasses (mainly composed of silicon dioxide, containing oxides such as heavy metals, boron and aluminum as necessary), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.) Conventionally known materials such as activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, and hydroxyapatite can be used. In addition, an organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers in advance to form a paste, polymerizing and curing, and pulverizing may be used. These fillers are used in one kind or a combination of several kinds, and the blending amount thereof may be appropriately determined in consideration of the operability (viscosity) and mechanical strength of the paste. It is 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, and more preferably 100 to 600 parts by weight with respect to 100 parts by weight of all components other than the filler.

  Among such inorganic fillers, when an inorganic filler having an X-ray contrast property with a refractive index of 1.5 to 1.6 is blended, a dental composite resin useful as a crown restoration material is obtained. Important physical properties desired for a composite resin for a crown include transparency and X-ray contrast properties similar to those of natural teeth. Transparency is achieved by matching the refractive indexes after curing of the inorganic filler and the polymerizable monomer as much as possible. In order to impart X-ray contrast properties, inorganic oxides having heavy metal elements such as zirconia, barium, titanium and lanthanum have been used as inorganic fillers. The refractive index of the inorganic filler containing such a heavy metal element is usually high and is in the range of 1.5 to 1.6. Since the polymerizable monomer (1) used in the dental composition of the present invention has one or more benzene skeletons in the molecule, the refractive index after curing is relatively high, and the refractive index is 1.52 or more. Have. Accordingly, when combined with such an inorganic filler having a high refractive index and having such an X-ray contrast property, the refractive index difference can be reduced, so that high transparency can be easily obtained.

  Examples of the inorganic filler include barium borosilicate glass (for example, Kimble Raysorb T3000, Shot 8235, Shot GM27884, Shot GM39923), strontium boroaluminosilicate glass (for example, Raythorb T4000, Shot G018-093, Shot GM32087), and lanthanum glass. (Shot GM31684), fluoroaluminosilicate glass (for example, shot G018-091, shot G018-117) and the like.

  In the dental composition of the present invention, a composition containing a microfiller having a particle size of 0.1 μm or less is one of suitable embodiments for a dental composite resin. As the material of the filler having such a small particle size, silica (for example, trade name Aerosil), alumina, zirconia, titania and the like are preferable. The blending of such an inorganic filler having a small particle diameter is advantageous in obtaining polishing smoothness of the cured composite resin.

  These fillers may be subjected to surface treatment with a silane coupling agent or the like depending on the purpose. Examples of the surface treatment agent include known silane coupling agents such as γ-methacryloxyalkyltrimethoxysilane (carbon number between methacryloxy group and silicon atom: 3 to 12), γ-methacryloxyalkyltriethoxy. Organosilicon compounds such as silane (carbon number between methacryloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinylethoxysilane, and vinyltriacetoxysilane are used. The concentration of the surface treatment agent is usually in the range of 0.1 to 20% by weight, preferably 1 to 5% by weight with respect to the filler.

  In the dental composition of the present invention, in addition to the polymerizable monomer (1) as described above, a known polymerizable monomer can be used in combination as necessary.

  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. And esters such as (meth) acrylamide, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. Among them, (meth) acrylic acid esters are preferably used. Examples of such polymerizable monomers are shown below.

  In the present invention, a monomer having one olefinic double bond is a monofunctional monomer. Similarly, bifunctional monomers for two olefinic double bonds and trifunctional monomers for three.

(I) Monofunctional monomer: methyl (meth) acrylate, iso-butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) Acrylate, 2,3-dibromopropyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene Glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) Meth) acrylamide, (meth) acryloyloxydodecyl pyridinium bromide, (meth) acryloyloxy-dodecyl pyridinium chloride, and (meth) acryloyloxy hexadecyl pyridinium chloride or the like.

(B) Bifunctional monomer: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl methacrylate (2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane; commonly known as BisGMA) 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- (3-acryloyl) Oxy-2-hydroxypropoxy ) Phenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) ) Dimethacrylate (commonly known as UDMA).

(C) Monofunctional or higher monomers: trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N '-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyl And oxymethyl-4-oxyheptane.

  Moreover, when using the dental composition of this invention as a dental adhesive, various adhesive monomers as a monomer to copolymerize, especially the monomer which has an acidic group in a molecule | numerator are further mix | blended. The monomer having an acidic group is a compound having an acidic group and a polymerizable group in the same molecule, and examples of the acidic group include a phosphate residue, a pyrophosphate residue, a thiophosphate residue, and a carboxylic acid residue. Or the compound which has a sulfonic acid residue etc. and has a acryloyl group, a methacryloyl group, a vinyl group, a styrene group etc. as a polymeric group is mentioned.

  Examples of the polymerizable monomer having a phosphoric acid residue include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl. Dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen Phosphate, 2- (meth) acryloyloxyethylphenyl phosphoric acid, 2- (meth) acryloyloxyethyl 2′-bromoethyl phosphoric acid, (meth) acryloyloxyethyl phenylphosphonate, etc., and their acid chlorides Can be mentioned.

  Examples of the polymerizable monomer having a pyrophosphate residue include di (2- (meth) acryloyloxyethyl) pyrophosphate and the like and acid chlorides thereof. Examples of the polymerizable monomer having a thiophosphoric acid residue include 2- (meth) acryloyloxyethyl dihydrogen dithiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, and their acid chlorides. Things.

  Examples of the polymerizable monomer having a carboxylic acid residue include 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 5- (meth) acryloylaminopentylcarboxylic acid, 11- (meth) acryloyloxy-1,1. -Undecanedicarboxylic acid etc. and these acid chlorides or acid anhydrides are mentioned.

  Examples of the polymerizable monomer having a sulfonic acid residue include 2- (meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate and the like. These polymerizable monomers having an acidic group are used alone or in combination of several kinds.

  The compounding amount of these polymerizable monomers is usually used in a range not exceeding 100 parts by weight with respect to 100 parts by weight of the polymerizable monomer (1).

  In the dental composition of the present invention, in addition to the polymerizable monomer, the polymerization initiator, and the filler, additives such as a polymerization inhibitor, an ultraviolet absorber, a fluorescent agent, a pigment, and the like do not impair the effects of the present invention. You may contain.

  Examples of the polymerization inhibitor include 2,6-dibutylhydroxytoluene, hydroquinone, dibutylhydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone monomethyl ether, 2,6-di-t-butylphenol, and the like. You may mix | blend a seed or more.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, the abbreviations of the compounds used in the text and in the examples are as follows.

Polymerizable monomer 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (hereinafter abbreviated as Bis-GMA)
2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (hereinafter abbreviated as UDMA)
Triethylene glycol dimethacrylate (hereinafter abbreviated as 3G)
1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetraphenyldisiloxane (hereinafter abbreviated as Bis-TPS)

1,3-bis (3-methacryloyloxypropyl) -1,3-dimethyl-1,3-diphenyldisiloxane (hereinafter abbreviated as Bis-DPDMS)

1,3-bis (3-methacryloyloxypropyl) -1,3-diethyl-1,3-diphenyldisiloxane (hereinafter abbreviated as Bis-DPDES)

1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetrakis (4-methylphenyl) disiloxane (hereinafter abbreviated as Bis-TMPS)

1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetrakis (4-bromophenyl) disiloxane (hereinafter abbreviated as Bis-TBPS)

1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetrakis (pentafluorophenyl) disiloxane (hereinafter abbreviated as Bis-TFPS)

1,3-bis [3- (2-methacryloyloxyethyloxy) propyl] -1,1,3,3-tetraphenyldisiloxane (hereinafter abbreviated as Bis-TPES)

1,3-bis (6-methacryloyloxyhexyl) -1,1,3,3-tetraphenyldisiloxane (hereinafter abbreviated as Bis-TPHS)

1,3-bis (11-methacryloyloxyundecyl) -1,1,3,3-tetraphenyldisiloxane (hereinafter abbreviated as Bis-TPUS)

1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetramethyldisiloxane (hereinafter abbreviated as Bis-TMS)

1,3-bis [(p-acryloxymethyl) phenethyl] -1,1,3,3-tetramethyldisiloxane (hereinafter abbreviated as Bis-TMPSA)

Polymerization initiator camphor-quinone (hereinafter abbreviated as CQ)

Amine ethyl N, N-dimethylaminobenzoate (hereinafter abbreviated as PDE)

Polymerization inhibitor 2,6-dibutylhydroxytoluene (hereinafter abbreviated as BHT)
Hydroquinone monomethyl ether (hereinafter abbreviated as MEHQ)

Moreover, the evaluation method of physical properties in Examples and Comparative Examples ( ¹ H-, ¹³ C-nuclear magnetic resonance spectrum, refractive index, cured body strength (bending strength), consistency, and linear polymerization shrinkage) is as follows. .

(1) Nuclear magnetic resonance (NMR) spectrum
¹ H-NMR and ¹³ C-NMR spectra were measured at 270 MHz and 68 MHz, respectively, using a JNM-GSX270 spectrometer manufactured by JEOL Ltd. Deuterated chloroform was used as a solvent, and tetramethylsilane (TMS) was added as an internal standard.

(2) Refractive index The refractive index was measured using an Atago Co., Ltd. Abbe refractometer. Bromonaphthalene was used as an intermediate solution. The monomer (liquid) was measured as it was. In addition, the polymer was blended with 0.5 wt% of TMDPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) with respect to the monomer and poured into a circular mold, and irradiated with light for 3 minutes (Morita, α Light IIN). Then, the polymerized product was measured. The measurement was performed in a constant temperature room at 25 ° C.

(3) Measurement of mechanical strength of the cured product (bending strength)
After filling the composite resin paste into a stainless steel mold (dimensions 2 mm x 2 mm x 30 mm), press the top and bottom with a slide glass and irradiate light from both sides with a light irradiator (Morita, α Light IIN) for 2 minutes each. And cured. About each Example and the comparative example, 5 hardened | cured material was produced for every one, and after taking out from a metal mold | die, hardened | cured material was stored for 24 hours in 37 degreeC distilled water. Using an autograph AG-I 100KN manufactured by Shimadzu Corporation, the bending strength was measured under the conditions of span: 20 mm, crosshead speed: 1 mm / min, and the average value of the measured values of each test piece was calculated. And bending strength.

(4) Consistency of paste 0.5 cc of composite resin paste was measured, and a 1 kg load was applied to the composite resin paste through a glass plate for 30 seconds to crush the paste. The maximum diameter and the minimum diameter of the spread disc-shaped paste were measured, and the average value (mm) of the two points was taken as the consistency. The greater the consistency, the softer the paste, and the higher the filler content of the composite resin.

(5) Transparency A composite resin paste was placed on a glass plate, a metal spacer having a thickness of 1 mm was placed on both sides of the paste, and another glass plate was placed from above and pressed to cure the paste. A standard white board and a standard blackboard are placed on the background of a 1 mm thick cured product, and a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) is used according to the L * a * b * color system in each background using D65 / 2 as the light source. : Σ90). In L * representing lightness, when the background white is L * (white) and the background black is L * (black), it is defined as ΔL * = L * (white) −L * (black). Since the value of ΔL * increases as the transparency increases, ΔL * is used as an index representing transparency.

(6) Measurement of linear polymerization shrinkage The following measurement was performed with reference to Akihiko Watanabe, Masahiro Nagai, Kazunari Akiyoshi, Dental Materials and Instruments, 25, 120 (2005). A stainless steel mold (thickness 3 mm, diameter 6 mm hole) was placed on the cover glass as a mold, and cocoa butter (made by GC Corporation) was applied to the wall of the mold hole. The mold hole was filled with a composite resin and the surface was leveled with a razor. In the middle of the filled resin, an aluminum disc (laser light reflector) having a diameter of 3 mm was placed and placed on a set table (slide glass). The center of the reflector was irradiated with red laser light for displacement measurement, and left for a while until the measured value was stabilized. After the measurement value was stabilized, light was irradiated for 60 seconds from below the slide glass with a jet light. Measurement was performed for 15 minutes from the start of light irradiation while recording the displacement of the reflector. After the measurement was completed, the resin was removed from the mold and the thickness was measured. The linear shrinkage rate was calculated from the displacement of the reflector after light irradiation and the thickness of the cured resin. The measurement was performed 4 times or more, and the average value was defined as the linear polymerization shrinkage. When Δl is the displacement of the resin measured with a laser displacement meter and l is the thickness of the resin after polymerization, the linear polymerization shrinkage can be calculated from the following equation.

[Synthesis Example 1-1]
Synthesis of undecenyl methacrylate The synthesis was performed as follows with reference to Japanese Patent Application Laid-Open No. 2004-210665. Into a 2 L four-necked flask equipped with a stirrer, air bubbling tube, dehydration tube, and cooling tube was placed 34 g of undecenol (manufactured by Toyokuni Seiyaku Co., Ltd.) and 21 g of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.). 1.2 g of toluenesulfonic acid and 0.1 g of hydroquinone monomethyl ether were added, and a dehydration reaction was performed at 130 to 140 ° C. The reaction was completed in about 2 hours. The reaction crude liquid was washed with an aqueous alkali solution and further washed twice with water, and then the solvent was removed by an evaporator while bubbling with air to obtain a purified product. ¹ H-NMR measurement was performed, and it was confirmed from the chemical shift value and the integral value that the obtained colorless and transparent liquid was the target compound. The yield was 37.1 g, and the yield was 78%.

[Synthesis Example 1-2]
Synthesis of hexenyl methacrylate By using 5-hexen-1-ol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of undecenol described in Synthesis Example 1-1, the same synthesis operation as in Synthesis Example 1-1 was performed, thereby methacrylic acid. Hexenyl was obtained. The chemical reaction formula of this synthesis example is shown below.

[Synthesis Example 2-1]
Synthesis of Bis-TPS 15.13 g (120 mmol) of allyl methacrylate was weighed in a 200 mL eggplant flask, and 200 mg of MEHQ was added and stirred. A drop of catalyst (Platinum-Divinyltetramethyl Diloxane Complex) was added thereto with a dropper. Strauss, et al. Am. Chem. Soc. , 112, 2673-2681 (1990), and 11.48 g (0.03 mol) of Ph ₂ HSiOSiHPh ₂ was added every 15 minutes in four quarters. One drop of catalyst was added after the third and fourth injections of Ph ₂ HSiOSiHPh ₂ , and the reaction was carried out with stirring at room temperature (23 ° C.). Thereafter, 2 drops of the catalyst were added 3 days and 6 days after the start of the reaction. After stirring at room temperature for 7 days, the reaction solution was dissolved in hexane, and the reaction was terminated by deactivating the catalyst with 1N HCl. The reaction mixture was transferred to a 300 mL separatory funnel, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Next, after adding anhydrous sodium sulfate to the washed organic layer and drying, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a yellow liquid concentrated residue. The resulting concentrated residue was purified using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 10/1) to remove oily impurities mixed in the residue. After the column purification, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a colorless and transparent liquid. ¹ H-NMR measurement was performed, and it was confirmed from the chemical shift value and the integral value that the obtained colorless and transparent liquid was the target compound. The yield was 4.21 g and the yield was 22%. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.08 (m, 4H), 1.58 (m, 4H), 1.87 (s, 6H), 3.94 (dd, 4H), 5.48 ( s, 2H), 6.00 (s, 2H), 7.30 (m, 12H), 7.44 (m, 8H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 11.8, 18.2, 22.7, 66.8, 124.8, 127.8, 129.8, 134.4, 135.9, 136.6 157.2 (ppm)
Refractive index: (monomer) 1.564
(Polymer) 1.599

[Synthesis Example 2-2]
Synthesis of Bis-DPDMS A synthetic operation similar to that of Synthesis Example 2-1 was performed by using Ph (CH ₃ ) HSiOSiH (CH ₃ ) Ph instead of Ph ₂ HSiOSiHPh ₂ described in Synthesis Example 2-1 to perform Bis-DPDMS. Got. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 0.66 (s, 6H), δ 1.08 (m, 4H), 1.58 (m, 4H), 1.87 (s, 6H), 3.94 ( dd, 4H), 5.48 (s, 2H), 6.00 (s, 2H), 7.30 (m, 6H), 7.44 (m, 4H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 1.6, 11.8, 18.2, 22.7, 66.8, 124.8, 127.8, 129.8, 134.4, 135.9, 136.6, 157.2 (ppm)
Refractive index: (monomer) 1.533
(Polymer) 1.559

[Synthesis Example 2-3]
Synthesis of Bis-DPDES A synthetic operation similar to that of Synthesis Example 2-1 is performed using Ph (CH ₂ CH ₃ ) HSiOSiH (CH ₂ CH ₃ ) Ph instead of Ph ₂ HSiOSiHPh ₂ described in Synthesis Example 2-1. Bis-DPDES was obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 0.90 (m, 6H), δ 1.06 (m, 4H), 1.49 (s, 6H), 1.57 (m, 4H), 1.88 ( s, 6H), 3.96 (dd, 4H), 5.48 (s, 2H), 6.03 (s, 2H), 7.31 (m, 6H), 7.45 (m, 4H) ( ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 5.4, 8.4, 11.7, 18.3, 22.7, 67.0, 124.9, 127.6, 129.7, 134.5, 136.0, 136.7, 157.4 (ppm)
Refractive index: (monomer) 1.527
(Polymer) 1.552

[Synthesis Example 2-4]
Synthesis of Bis-TMPS A synthetic operation similar to that of Synthesis Example 2-1 was performed using [Ph (CH ₃ )] ₂ HSiOSiH [Ph (CH ₃ )] ₂ instead of Ph ₂ HSiOSiHPh ₂ described in Synthesis Example 2-1. Bis-TMPS was obtained by performing. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.07 (m, 4H), 1.58 (m, 4H), 1.88 (s, 6H), 2.05 (s, 3H), 3.93 ( dd, 4H), 5.48 (s, 2H), 6.02 (s, 2H), 7.25 (m, 8H), 7.39 (m, 8H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 11.8, 18.2, 20.9, 22.7, 66.8, 124.8, 127.8, 129.8, 134.4, 135.9, 138.6, 157.2 (ppm)
Refractive index: (monomer) 1.555
(Polymer) 1.587

[Synthesis Example 2-5]
Synthesis of Bis-TBPS A synthetic operation similar to that of Synthesis Example 2-1 is performed using [Ph (Br)] ₂ HSiOSiH [Ph (Br)] ₂ instead of Ph ₂ HSiOSiHPh ₂ described in Synthesis Example 2-1. Bis-TBPS was obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.06 (m, 4H), 1.59 (m, 4H), 1.88 (s, 6H), 3.96 (dd, 4H), 5.48 ( s, 2H), 6.04 (s, 2H), 7.44 (m, 8H), 7.54 (m, 8H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 11.8, 18.2, 22.9, 66.7, 124.5, 127.8, 129.8, 134.4, 135.9, 138.1 157.2 (ppm)
Refractive index: (monomer) 1.571
(Polymer) 1.606

[Synthesis Example 2-6]
Synthesis of Bis-TFPS Using [Ph (F ₅ )] ₂ HSiOSiH [Ph (F ₅ )] ₂ instead of Ph ₂ HSiOSiHPh ₂ described in Synthesis Example 2-1, the same synthetic operation as in Synthesis Example 2-1 was performed. By performing, Bis-TBPS was obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.08 (m, 4H), 1.59 (m, 4H), 1.86 (s, 6H), 3.94 (dd, 4H), 5.48 ( s, 2H), 5.99 (s, 2H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 11.6, 18.2, 22.7, 66.8, 124.8, 132.9, 134.4, 135.9, 136.6, 140.6, 157.2 (ppm)
Refractive index: (monomer) 1.576
(Polymer) 1.608

[Synthesis Example 2-7]
Synthesis of Bis-TPES By using 2-allyloxyethyl methacrylate (Monomer-Polymer & Dajac Laboratories, INC) in place of allyl methacrylate described in Synthesis Example 2-1, the same synthetic operation as in Synthesis Example 2-1 was performed to perform Bis-TPES. TPES was obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.08 (m, 4H), 1.58 (m, 4H), 1.87 (s, 6H), 3.37 (dd, 4H), 3.65 ( dd, 4H), 3.94 (dd, 4H), 5.48 (s, 2H), 6.00 (s, 2H), 7.30 (m, 12H), 7.44 (m, 8H) ( ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 11.8, 18.2, 22.7, 66.8, 69.9, 73.1, 124.8, 127.8, 129.8, 134.4 135.9, 136.6, 157.2 (ppm)
Refractive index: (monomer) 1.559
(Polymer) 1.581

[Synthesis Example 2-8]
Synthesis of Bis-TPHS Bis-TPHS was synthesized by performing the same synthesis operation as in Synthesis Example 2-1 using hexenyl methacrylate obtained in Synthesis Example 1-2 instead of allyl methacrylate described in Synthesis Example 2-1. Obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ0.75 (m, 4H), 1.24 (s, 12H), 1.66 (m, 4H), 1.92 (s, 6H), 4.11 ( dd, 4H), 5.53 (s, 2H), 6.11 (s, 2H), 7.29 (m, 12H), 7.44 (m, 8H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 14.6, 18.4, 22.5, 23.9, 26.0, 28.8, 29.4, 29.5, 33.5, 65.0, 67.4, 124.6, 127.7, 128.9, 129.1, 133.3, 134.2, 136.7, 136.6, 167.5 (ppm)
Refractive index: (monomer) 1.558
(Polymer) 1.586

[Synthesis Example 2-9]
Synthesis of Bis-TPUS Bis-TPUS was synthesized by performing the same synthesis operation as in Synthesis Example 2-1 using undecenyl methacrylate obtained in Synthesis Example 1-1 instead of allyl methacrylate described in Synthesis Example 2-1. Obtained. The chemical reaction formula of this synthesis example is shown below.

The ¹ H-NMR, ¹³ C-NMR, and refractive index data of the compound obtained by the above method were as follows.
¹ H-NMR (270 MHz CDCl ₃ ): δ 0.73 (m, 4H), 1.23 (s, 32H), 1.66 (m, 4H), 1.93 (s, 6H), 4.13 ( dd, 4H), 5.53 (s, 2H), 6.10 (s, 2H), 7.30 (m, 12H), 7.44 (m, 8H) (ppm)
¹³ C-NMR (100 MHz CDCl ₃ ): δ 14.4, 18.2, 22.3, 23.9, 26.1, 28.8, 29.3, 29.6, 33.7, 64.9, 67.1, 124.7, 127.7, 128.6, 129.2, 133.3, 134.4, 136.6, 136.8, 167.3 (ppm)
Refractive index: (monomer) 1.551
(Polymer) 1.578

[Example 1]
In 100 parts by weight of Bis-TPS synthesized in Synthesis Example 2-1, 0.5 part by weight of CQ, 0.05 part by weight of BHT and 1.0 part by weight of PDE were uniformly dissolved as a photopolymerization catalyst, and photopolymerizable polymerizability. A monomer composition was prepared. Furthermore, 100 parts by weight of the polymerizable monomer composition was silica powder obtained by silane treatment with γ-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as γ-MPS) (Nippon Aerosil Co., Ltd., Aerosil 130, average particle size 0.020 μm). ) 40 parts by weight and 530 parts by weight of barium glass silane-treated with γ-MPS (Shot 8235, average particle size 2.5 μm) were kneaded to obtain a dental composition, which was used as a dental composite resin. did. In the silane treatment, for silica powder, 100 g of silica powder, 40.0 g of γ-MPS, 0.16 g of acetic acid, and 80 mL of distilled water were placed in a beaker and stirred at room temperature for 1 hour, and the water was removed by lyophilization. Then, it carried out by heating at 90 degreeC for 3 hours. Moreover, about barium glass, it carried out similarly to the silane process of a silica powder using 100g of barium glass, 1.0g of (gamma) -MPS, 0.16g of acetic acid, and 80mL of distilled water. The consistency of the dental composite resin was measured, and the bending strength, elastic modulus, transparency, and linear polymerization shrinkage of the cured product were measured. The measurement results are shown in Table 1.

[Examples 2 to 9]
In Example 1, instead of Bis-TPS, Bis-DPDMS (Example 2), Bis-DPDES (Example 3), Bis-TMPS (Example 4), Bis-TBPS (Example 5), Bis- A dental composite having the same composition as in Example 1 except that TFPS (Example 6), Bis-TPES (Example 7), Bis-TPHS (Example 8), and Bis-TPUS (Example 9) were used. A resin was prepared. The consistency of the composite resin was measured, and the cured product was measured for bending strength, elastic modulus, transparency, and linear polymerization shrinkage. The measurement results are shown in Table 1.

[Comparative Example 1]
In Example 1, a dental composite resin having the same composition as in Example 1 was prepared except that Bis-TMS (Gelest) was used instead of Bis-TPS. The consistency of the composite resin was measured, and the cured product was measured for bending strength, elastic modulus, transparency, and linear polymerization shrinkage. The measurement results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 1, a dental composite resin having the same composition as Comparative Example 1 was prepared, except that Bis-TMPSA (United Chemical Technologies) was used instead of Bis-TMS. The consistency of the composite resin was measured, and the cured product was measured for bending strength, elastic modulus, transparency, and linear polymerization shrinkage. The measurement results are shown in Table 1.

[Comparative Examples 3 to 5]
In Comparative Example 1, Bis-GMA (Comparative Example 3), Bis-GMA (50 parts by weight) and 3G (50 parts by weight) (Comparative Example 4), and UDMA (Comparative Example 5) were used instead of Bis-TMS. A dental composite resin having the same composition as that of Comparative Example 1 was prepared except that. The consistency of the composite resin was measured, and the cured product was measured for bending strength, elastic modulus, transparency, and linear polymerization shrinkage. The measurement results are shown in Table 1.

  From Table 1, the dental composite resin of Example 1 using Bis-TPS as a polymerizable monomer showed excellent mechanical properties with a bending strength of 124 MPa and an elastic modulus of 14.5 Mpa. Also, the linear polymerization shrinkage was small and the consistency was in a good range. That is, it had good physical properties in a balanced manner with respect to mechanical strength, polymerization shrinkage and viscosity.

  Similarly, Bis-DPDMS (Example 2), Bis-DPDES (Example 3), Bis-TMPS (Example 4), Bis-TBPS (Example 5), Bis-TFPS (Example 6), Bis-TPES As for (Example 7), Bis-TPHS (Example 8), and Bis-TPUS (Example 9), the composite resin using them had balanced physical properties.

  In addition, the polymerizable monomers of Synthesis Examples 2-1 to 2-9 had a high refractive index, and all of the polymers had a refractive index of 1.55 or more. Therefore, when these polymerizable monomers are combined with an inorganic filler having a high refractive index such as barium glass and having a high refractive index, the difference in refractive index can be adjusted to a small value. It can be said that high transparency can be obtained. Actually, even when the transparency of the composite resin containing the polymerizable monomers of Synthesis Examples 2-1 to 2-9 (composite resins of Examples 1 to 9) was evaluated, high transparency was obtained. .

  On the other hand, in Comparative Example 1 using Bis-TMS which is a polymerizable monomer having silicon similarly, both the bending strength and the elastic modulus are greatly inferior, and the linear polymerization shrinkage is also the same as that of the composite resin of the example. It was big compared. Also in Comparative Example 2 using Bis-TMPSA, the linear polymerization shrinkage ratio was larger than that of the composite resin of the example, and the refractive index of the polymer of Bis-TMPSA was also low, so high transparency could not be obtained. .

  In addition, with regard to Bis-GMA and UDMA that have been used in conventional dental composite resins alone, even when mixed with fillers, the familiarity of monomers and fillers is poor, and a paste-like composition cannot be obtained. A dental composite resin could not be produced.

  A dental composite resin (Comparative Example 4) prepared by using 3G as a diluent in combination with Bis-GMA has a bending strength equivalent to that of Examples 1 to 9, but a linear polymerization shrinkage of 1.49 (lin %), And the dental composite resin of the example was superior in balance.

  As described above, it is shown that when a dental composition containing the polymerizable monomer (1) is used for a composite resin, a cured product having a low polymerization shrinkage ratio and excellent in aesthetics and mechanical properties can be obtained. It was done.

Claims (9)

The following general formula (1)

{Wherein R ¹ , R ² , R ³ and R ⁴ represent the following general formula (2)

(Wherein Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms)
Or an alkyl group having 1 to 6 carbon atoms, at least one of which is a group represented by the general formula (2),
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group,
X ¹ and X ² are each independently an oxygen atom, a sulfur atom or NH,
k and l are each independently an integer of 2 to 12, and m and n are each independently an integer of 0 to 4}
A dental composition comprising a polymerizable monomer represented by the formula: The dental composition according to claim 1, wherein at least one of R ¹ and R ³ and at least one of R ² and R ⁴ are a group represented by the general formula (2). The dental composition of claim ² , wherein R ¹ = R ³ and R ² = R ⁴ . ^{Y 1, Y 2, Y 3} , Y is ⁴ and Y ⁵ is hydrogen atom, a dental composition according to any one of claims 1 to 3. The dental composition according to any one of claims 1 to 4, wherein X ¹ and X ² are oxygen atoms, and m and n are 0.   The dental composition according to any one of claims 1 to 5, wherein k and l are each independently an integer of 2 to 6.   Furthermore, the dental composition in any one of Claims 1-6 containing a polymerization initiator and a filler.   The dental composition according to claim 7, wherein the polymerization initiator is a photopolymerization initiator.   A composite resin using the dental composition according to claim 1.