JP5804807B2 - Dental filling restoration material - Google Patents

Description

  The present invention relates to a dental filling and restorative material. More specifically, the present invention relates to a dental filling and restorative material that has water repellency and that has a small polymerization shrinkage on the surface layer of the restorative material and can highly suppress secondary caries.

  In the restoration of a tooth damaged by caries, fracture or the like, a photocurable resin-based filling / restoration material generally called a composite resin is widely used because of its ease of operation and high aesthetics. The resin-based filling / restoring material is usually composed of a polymerizable composition containing a polymerizable monomer, a filler, and a polymerization initiator. However, when dental restoration is performed using such a resin-based filling restorative material, secondary caries may occur relatively early in the vicinity of the restoration site.

  In order to suppress the secondary caries, it is important not to allow plaques that cause caries to adhere to the vicinity of the joint between the cured body of the filling restoration material packed in the cavity and the peripheral teeth. As a method for suppressing the adhesion of plaque to the cured body of the resin-based filling / restoring material, it is effective to impart water repellency to the material. The method includes blending a fluorine-containing material into the resin-based filling / restoring material. Examples include a method using a fluorine group as at least a part of a polymerizable monomer (Patent Document 1), a method using a fluorinated resin powder as at least a part of a filler (Patent Document 2), and a filler. In addition, a technique (Patent Document 3) for performing a surface treatment with a silane coupling agent containing a fluorine group is known.

  However, it is difficult to suppress the occurrence of secondary caries to a high degree only by blending these fluorine-containing materials, and there is a demand for the development of a more effective preventive measure. As a measure for suppressing secondary caries other than the above-described provision of water repellency, reduction of polymerization shrinkage at the time of curing of the filling and restorative material may be mentioned.

  Here, as the polymerizable monomer for the resin-based filling / restoring material, a (meth) acrylate-based radical polymerizable monomer is widely used because of its good photopolymerizability. However, the radically polymerizable monomer is an addition polymerization type and has a problem that the polymerization shrinkage is inherently large due to its curing mechanism. Therefore, in the case of a tooth restoration, in the resin-based filling restoration material packed in the cavity, a gap is generated at the boundary with the surrounding teeth due to this polymerization shrinkage during curing. Thus, the plaque easily enters and sticks into such gaps, which causes secondary caries. Therefore, it is considered that the occurrence of secondary caries can be effectively suppressed by reducing the polymerization shrinkage of the resin-based filling / restoring material.

  In particular, in the filling restorative material packed in the cavity, the surface portion of the tooth (hereinafter referred to as the surface layer) is in a state where a gap is likely to occur at the boundary between the hardened body and the peripheral tooth. Accordingly, if there is a gap here, it tends to become the starting point of plaque adhesion, and secondary caries will occur remarkably, so it is most important how to suppress polymerization shrinkage on the surface layer.

  Several means for suppressing polymerization shrinkage of the resin-based filling / restoring material are known, and one of them is a method of containing a dendritic polymer (Patent Documents 4 to 8). Here, the dendritic polymer is a polymer in which the molecular chain has many branches, and has a particle shape close to a sphere. For this reason, when the polymer is dissolved in the solution, the increase in the viscosity of the dendritic polymer is smaller than that of a general polymer. Therefore, when a dendritic polymer is used as a constituent material of a dental filling restorative material, a large amount of dendritic polymer is contained in the dental filling restorative material without greatly changing the filling rate of the filler and the operability of the material. Can be added. That is, it becomes easy to relatively increase the blending ratio of the dendritic polymer as a constituent component in the dental filling and restorative material and to relatively decrease the blending ratio of the polymerizable composition instead. By doing so, the dendritic polymer basically does not cause a large polymerization shrinkage due to the polymerization like a polymerizable monomer, so the polymerization shrinkage rate when the dental filling restorative material is cured is kept small. Can do.

  However, even if the polymerization shrinkage rate is reduced by the method of containing the dendritic polymer, a gap is formed at the boundary between the cured body and the peripheral teeth on the surface of the filling restoration material packed in the cavity. The actual situation is that it has not yet been sufficiently suppressed, and the occurrence of secondary caries has not been highly prevented.

JP 2003-81731 A JP 2005-35940 A JP 2007-238567 JP-A-8-231864 Special table 2001-509179 Japanese Patent No. 3971307 JP 2006-298919 A WO03 / 013379

  As described above, the conventionally known measures for suppressing secondary caries have not yet been sufficiently effective in either a method for imparting water repellency to a dental filling restorative material or a method for reducing polymerization shrinkage. In particular, when packed in the cavity, the polymerization shrinkage on the surface layer cannot be suppressed to a high degree, and a gap is formed at the boundary between the hardened body and the peripheral teeth, and plaque adheres to the secondary surface. It was not possible to prevent the occurrence of caries at a satisfactory level. Therefore, an object of the present invention is to provide a dental filling and restorative material that highly suppresses polymerization shrinkage on the surface layer surface, has a high effect of preventing plaque adhesion, and is less susceptible to secondary caries.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by blending a dendritic polymer having a fluorine group into a dental filling restorative material, and the present invention has been completed.

That is, the present invention, (A) a polymerizable monomer, Ri Na contain (B) dendritic polymer having a fluorine group, (C) a polymerization initiator, and (D) a filler, and the (B ) The dendritic polymer having a fluorine group has a hydrodynamic average diameter in tetrahydrofuran of 1 to 40 nm, a mass average molecular weight of 5,000 to 50,000, and CH ₂ I _{2 as} measured by dynamic light scattering. The dental filling restoration material has a contact angle (23 ° C.) to 60 ° to 130 ° and a contact angle to water (23 ° C.) of 80 ° to 130 ° .

  The dental filling / restoring material of the present invention has a small polymerization shrinkage at the time of curing, and in particular, when packed in a cavity, it can highly suppress the polymerization shrinkage on the surface layer. Therefore, in the surface layer surface, it is possible to suppress a gap from being formed at the boundary between the cured body and the peripheral teeth, and it is possible to prevent the plaque from adhering from the gap as a starting point. In addition, the cured body of the filling / restoring material itself has high water repellency and is in a state in which the plaque is hardly attached due to the material. Therefore, as a result of these effects acting synergistically, when a tooth is restored using the filling and restorative material of the present invention, the occurrence of secondary caries can be significantly suppressed.

  In the dental filling and restorative material of the present invention, a dendritic polymer having a fluorine group is blended. The reason why it becomes possible to highly suppress polymerization shrinkage on the surface layer when filling the dental filling / restoration material in the cavity is not necessarily clear, but the present inventors have the following action. I guess. That is, since the dendritic polymer has a particle shape such as a nearly spherical shape, the dendritic polymer originally has little interaction with other components and is easily moved in the paste. In addition, since the dendritic polymer used in the present invention has a fluorine group in the molecule, it has higher oil repellency and lower surface free energy than ordinary hydrocarbon-based dendritic polymers. The ease of movement in the paste is further improved. As a result, the dendritic polymer is easily extruded to the surface layer when the dental filling / restoring material is cured, and the effect of preventing the adhesion of plaque on the surface layer is remarkably enhanced, and further, the effect of suppressing the polymerization shrinkage at this site is also achieved. I think it will increase locally.

  Hereinafter, each component of (A) a polymerizable monomer, (B) a dendritic polymer having a fluorine group, (C) a polymerization initiator, and (D) a filler constituting the dental filling / restoring material of the present invention. Will be described sequentially.

(A) Polymerizable monomer As the polymerizable monomer (A) blended in the dental filling / restoring material of the present invention, known monomers used in various curable compositions can be used without particular limitation. . For general dental use, those having a refractive index at 25 ° C. in the range of 1.4 to 1.7 are preferably used. As such a polymerizable monomer, it is preferable to use a (meth) acrylic radical polymerizable monomer. Specific examples of the (meth) acrylic radical polymerizable monomer include those shown in the following (I) to (IV).

(I) Monofunctional monomer Methacrylate such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, acetoacetoxyethyl methacrylate, propionyloxyethyl methacrylate, glycidyl methacrylate, etc., and these methacrylates Acrylate; or acrylic acid, methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid, and anhydride, 6-methacryloyl Oxyhexamethylenemalonic acid, 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl Acid group-containing polymerizable monomers, such as rudihydrogen phosphate, 10-methacryloyloxydecamethylene dihydrogen phosphate, and 2-hydroxyethyl hydrogen phenyl phosphate.

(II) Bifunctional polymerizable monomer (i) Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxy Phenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 ( 4-Methacryloyloxydiethoxyphenyl) -2 (4-me Tacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2, 2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, etc. Corresponding vinyl monomers having —OH groups such as acrylates and aromatic monomers such as diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate. Diaducts obtained from addition with a diisocyanate compound having an aromatic group.

(Ii) Aliphatic compound-based ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate Such as methacrylates or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and hexamethylene Diadducts obtained from adducts with diisocyanate compounds such as isocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2-hydroxy Propoxy) ethyl and the like.
(III) Trifunctional polymerizable monomer: Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

(IV) Tetrafunctional polymerizable monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4 Diadduct obtained from an adduct of a diisocyanate compound such as 1,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  These (meth) acrylic radical polymerizable monomers may be used alone or in combination of two or more.

  In addition to the (meth) acrylic radical polymerizable monomer, other than the above (meth) acrylic polymerizable monomer, for ease of polymerization, adjustment of viscosity, or adjustment of other physical properties. It is also possible to perform polymerization by mixing other polymerizable monomers. Examples of other polymerizable monomers include fumaric acid esters such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene, or α-methyl. Styrene derivatives; allyl compounds such as diallyl terephthalate, diallyl phthalate, diallyl diglycol carbonate, and the like.

(B) Dendritic polymer having a fluorine group The dendritic polymer is a polymer having many branched structures. The mass average molecular weight is 2000 or more as measured by GPC (Gel Permeation Chromatography) method, more preferably in the range of 2000 to 300000, and still more preferably in the range of 5000 to 50000. And since it has many branch structures with this mass average molecular weight, dendritic polymer | macromolecule is not string-like like a normal polymer | macromolecule, but has the shape of particles, such as a near spherical shape. The hydrodynamic average diameter in tetrahydrofuran measured by the dynamic light scattering method is usually 1 to 40 nm, and more effectively exhibits the effect of reducing polymerization shrinkage at the time of curing. From the viewpoint of maintaining good operability, the thickness is preferably 1 to 20 nm, and more preferably 1 to 10 nm.

  The hydrodynamic average diameter of the dendritic polymer is satisfied when the polymer satisfying the mass average molecular weight has a large number of branched structures, and the mass average molecular weight is too small or too large. In this case, as a matter of course, even if the mass average molecular weight is satisfied, if the branching is insufficient, the particle shape does not expand and the range is not reached.

  Dendritic polymers are roughly classified into dendrimers and hyperbranched polymers. Dendrimers have a precise chemical structure, and a branched structure is always introduced at a branchable site. On the other hand, the hyperbranched polymer may have partially missing portions, irregular or discontinuous portions in the branch repeating unit, and branch structures are not introduced in all branchable portions. Since dendrimers have precise targetivity and defect-free branching, they usually require precise control of synthesis, such as synthesis by repeated protection-deprotection, and are generally expensive due to the time and effort required for synthesis. . On the other hand, the hyperbranched polymer is easy to synthesize and can usually be synthesized in one step. Therefore, since hyperbranched polymers can be synthesized easily and inexpensively, they are advantageous as dendritic polymers used for dental filling and restorative materials.

  In the present invention, the above dendritic polymer having a fluorine group is used. The fluorine group may be bonded to any position of the multiple branched structures. However, from the viewpoint of exposing the surface of the particles to better exhibit oil repellency and water repellency, at least at the end of each branched chain. Bonding is preferred. The amount of fluorine group introduced is as high as possible from the viewpoint of enhancing the oil repellency of the dendritic polymer, facilitating extrusion to the surface of the dental restoration material, and highly suppressing polymerization shrinkage on the surface. It should be contained in a large number. However, even if it contains a large amount of fluorine groups, there is a possibility that the cured body of the dental filling and restorative material will deteriorate the familiarity with the dental adhesive and the tooth, reduce the adhesive force to the cavity and easily fall off. Because there is, attention is necessary. Furthermore, if the fluorine group content is too high, the refractive index of the dendritic polymer decreases, and it becomes opaque when a filling restorative material is prepared in combination with polymerizable monomers and fillers widely used in dental applications. It becomes a problem in terms of aesthetics.

From these, the dendritic polymer preferably has a fluorine group introduced and a contact angle (23 ° C.) with respect to CH ₂ I ₂ of 60 ° to 130 °, more preferably 70 ° to 100 °. In general, in a normal hydrocarbon-based dendritic polymer into which no fluorine group is introduced, the contact angle (23 ° C.) with respect to CH ₂ I ₂ is only about 30 ° to 40 °. The dendritic polymer used in the present invention has high water repellency due to the introduction of the fluorine group, and those having the oil repellency usually have a contact angle (23 ° C.) with respect to water of 80 ° to It is as large as 130 °, more preferably 90 ° to 120 °. Thereby, as mentioned above, when used for tooth restoration, an effect that plaque hardly adheres to the cured body is exhibited.

In the present invention, the contact angle of the dendritic polymer with respect to CH ₂ I ₂ or water is determined by drying the solvent on a hot plate at 150 ° C. after spin-coating a 5% toluene solution of the dendritic polymer on a Si wafer. 1 μl of CH ₂ I ₂ or water was dropped on the sample prepared by performing the above and the contact angle value measured about 5 seconds after dropping.

  The dendritic polymer preferably has a refractive index in the range of 1.4 to 1.7 at 25 ° C. Generally, the refractive index of the polymerizable monomer and filler mainly used for dental filling restorative materials is in the range of 1.4 to 1.7. Therefore, it is preferable that the refractive index of the dendritic polymer is in this range because the obtained dental filling / restoring material has excellent transparency.

  Thus, it can be confirmed, for example, by ion chromatography that the dendritic polymer used in the present invention contains a fluorine group. The fluorine content in the dendritic polymer measured by ion chromatography is preferably 1 to 40% by mass, more preferably 10 to 30% by mass.

Such a dendritic polymer having a fluorine group is a method of modifying the terminal or remaining chain of an existing dendritic polymer with the fluorine group itself (F ⁻ ) or a functional group having the fluorine group, It is obtained by synthesizing a dendritic polymer using a polymerizable monomer having a fluorine group. Examples of the functional group having a fluorine group include fluoroalkyl groups such as a trifluoromethyl group and a 2,2,2-trifluoroethyl group.

  As such a dendritic polymer having a fluorine group, for example, reported by Masayuki Haraguchi et al. As “Fluorine-based surface modifier“ HYPERTECH FA-200 ””, “Convertech”, September 2010 issue, page 98 Has been. Examples of commercially available products include HYPERTECH (registered trademark) / FA-200 (manufactured by Nissan Chemical Industries, Ltd.).

  In the dental filling restorative material, the blending amount of the dendritic polymer having such a fluorine group may be appropriately determined in consideration of polymerization shrinkage, water repellency, and further considering the operability of the paste. . When the dental filling / restoring material is cured, it is preferable to add 5 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer in order to sufficiently reduce the polymerization shrinkage including the surface layer packed in the cavity. In addition, if too much of a dendritic polymer having a fluorine group is added, the operability of the paste and the filler filling rate are adversely affected. Therefore, 100 parts by mass or less is blended with 100 parts by mass of the polymerizable monomer. Is preferred. In the present invention, a particularly preferable blending amount of the dendritic polymer having a fluorine group is 8 to 40 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

(C) Polymerization initiator In the dental filling and restorative material of the present invention, any known (C) polymerization initiator can be used without limitation. Polymerization methods for filling and restorative materials include reactions using light energy such as ultraviolet rays and visible light (hereinafter referred to as photopolymerization), chemical reactions between peroxides and accelerators, and heating. Depending on the method, the following various polymerization initiators may be appropriately selected and used.

  Examples of the polymerization initiator used for photopolymerization include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, benzophenone, and 4,4′- Benzophenones such as dimethylbenzophenone and 4-methacryloxybenzophenone, α-diketones such as diacetyl, 2,3-pentadionebenzyl, camphorquinone, 9,10-phenanthraquinone and 9,10-anthraquinone, 2,4 -Thioxanthone compounds such as diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dic Lolobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, 2, Acylphosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide can be used.

  Incidentally, a reducing agent is often added to the photopolymerization initiator. Examples thereof include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, and N-methyldiethanolamine. Aldehydes such as lauryl aldehyde, dimethylaminobenzaldehyde and terephthalaldehyde, and sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid and thiobenzoic acid.

  Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, and diisopropyl peroxydicarbonate. Peroxides, azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, triethanolamine tetraphenylborate And boron compounds such as 5-butyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and the like, and sulfinates such as sodium benzenesulfinate and sodium p-toluenesulfinate. .

Among these polymerization initiators, the use of a photopolymerization initiator is preferable from the viewpoint of easy operation during use, and camphorquinone, bis (2,4,6-trimethylbenzoyl) -phenyl is particularly preferable. Examples include phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenylphosphine oxide.

  These (C) polymerization initiators may be used alone or in admixture of two or more. The amount of the (C) polymerization initiator is not particularly limited as long as it is an effective amount, but is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer, More preferably, it is 3 parts by mass.

(D) Filler The filler contained in the dental filling / restoring material of the present invention exhibits a function of improving the strength of the cured product and suppressing polymerization shrinkage. As such a filler, one or more selected from inorganic fillers, organic fillers, and inorganic-organic composite fillers can be used as appropriate.

  Examples of the inorganic filler include periodic groups I, II, III, IV, transition metals and oxides thereof, fluorides, carbonates, sulfates, silicates, hydroxides, chlorides, sulfites, and phosphoric acids. And salts thereof, mixtures thereof, complex salts and the like. More specifically, amorphous silica, quartz, alumina, titania, zirconia, barium oxide, yttrium oxide, lanthanum oxide, ytterbium oxide and other inorganic oxides, silica-zirconia, silica-titania, silica-titania-barium oxide , Composite oxides such as silica-titania-zirconia, borosilicate glass, aluminosilicate glass, fluoroaluminosilicate glass, inorganic fluorides such as barium fluoride, strontium fluoride, yttrium fluoride, lanthanum fluoride, ytterbium fluoride, Examples thereof include inorganic carbonates such as calcium carbonate, magnesium carbonate, strontium carbonate and barium carbonate, and inorganic sulfates such as magnesium sulfate and barium sulfate.

  Examples of the organic filler include polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl (meth) acrylate / ethyl (meth) acrylate copolymer, methyl (meth) acrylate / butyl (meth) acrylate copolymer or methyl Non-crosslinkable polymer such as (meth) acrylate / styrene copolymer, methyl (meth) acrylate / ethylene glycol di (meth) acrylate copolymer, methyl (meth) acrylate / triethylene glycol di (meth) acrylate copolymer A (meth) acrylate polymer such as a copolymer or a copolymer of methyl (meth) acrylate and a butadiene monomer can be used.

  Furthermore, an organic-inorganic composite filler can also be suitably used. For example, it can be produced by pulverizing a cured product obtained by curing a polymerization curable composition containing a polymerizable monomer and an inorganic filler.

  As the raw material filler of the organic-inorganic composite filler (hereinafter abbreviated as “composite filler raw material filler”), any known filler that can be used as a dental composite restorative material can be used without any limitation. As an example of the composite filler raw material filler which can be used suitably, what was illustrated as an inorganic filler of the term of (D) filler is mentioned. These polymerizable monomers may be used alone or in combination with different types.

  Also, any known polymerizable monomer that can be used as a dental composite restorative material can be used for the organic-inorganic composite filler raw material polymerizable composition (hereinafter abbreviated as “composite filler raw material monomer”) without any limitation. It is. Examples of the composite filler raw material monomer that can be suitably used include those exemplified in the section of (A) polymerizable monomer. These polymerizable monomers may be used alone or in combination with different types.

  The composite filler is cured by polymerizing the composite filler raw material monomer, which is a component of the composite filler, and a known polymerization initiator is used as the polymerization initiator without any particular limitation. Generally, different types of polymerization initiators are used depending on the polymerization means of the polymerizable monomer. Examples of polymerization means include those based on light energy such as ultraviolet rays and visible light, those based on chemical reaction between peroxides and accelerators, and those based on heating. Various polymerization initiators shown below depending on the polymerization means employed. A suitable polymerization initiator may be appropriately selected from the above, but it is preferable to use a thermal polymerization initiator from the viewpoint that a cured product having a lower yellowness can be obtained. Examples of the polymerization initiator include those exemplified in the section of (C) polymerization initiator. These polymerization initiators may be used alone or in combination of two or more. The addition amount of the polymerization initiator may be selected according to the purpose, but is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the organic / inorganic filler raw material monomer, more preferably 0.1 to 5% by weight. Used in parts ratio.

  In the polymerization of the composite filler, a known additive may be added before the polymerization within a range not impairing the effects of the present invention. Examples of such additives include pigments, ultraviolet absorbers, and fluorescent pigments. In addition, for the purpose of further improving the strength of the cured body, an inorganic filler having an average particle size of more than 1 μm and / or an average particle size of less than 0.1 μm as long as the surface smoothness and wear resistance are not lowered. An inorganic filler may be added.

  The composite filler may be subjected to washing, decolorization, and surface treatment prior to mixing with an inorganic filler or a polymerizable monomer. In general, decolorization is performed by dispersing the organic-inorganic composite filler in an appropriate solvent, dissolving and stirring the peroxide, and optionally heating, and a known peroxide is preferably used as the peroxide. it can.

  By treating the filler with a surface treatment agent typified by a silane coupling agent, the affinity with the polymerizable monomer, the dispersibility in the polymerizable monomer, the mechanical strength and water resistance of the cured product are improved. Can be improved. Examples of silane coupling materials include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- Examples include methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and hexamethyldisilazane.

  The refractive index of the filler described above is not particularly limited. For general dental use, those having a refractive index at 25 ° C. in the range of 1.4 to 1.7 are preferably used. Moreover, there is no restriction | limiting in particular also about a shape or a particle diameter. The shape or particle size is appropriately selected and used, but the average particle size is usually 0.001 to 100 μm, particularly preferably 0.001 to 10 μm. Further, among the fillers described above, it is particularly preferable to use a spherical filler since the surface smoothness of the resulting cured body is increased and an excellent repair material can be obtained.

The ratio of these fillers is required for dental filling and restorative materials. In addition to the strength of the cured product and small polymerization shrinkage, the viscosity (operability) when mixed with a polymerizable monomer and the mechanical properties of the cured product. Although it may be determined appropriately in consideration of physical properties, it is generally 50 to 1500 parts by mass, preferably 60 to 1000 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the filler content is small, the polymerization shrinkage becomes small, and a gap is likely to occur at the boundary between the cured body and the peripheral teeth, and the effect of the present invention for preventing this will be more significantly exhibited. The filler content is particularly preferably in the range of 70 to 600 parts by mass.

  The dental filling / restoration material of the present invention may be added with pigments, fluorescent pigments, dyes, UV absorbers to prevent discoloration to ultraviolet rays in order to match the color tone of the tooth, You may mix | blend a well-known additive as a component in the range which does not affect the effect of this invention.

  In the filling and restorative material, the mixing method of each component described above may be in accordance with a known filling and restorative material manufacturing method. In general, until all the components to be blended are weighed under red light until uniform. Mix well.

EXAMPLES Hereinafter, although an Example is given and this invention is shown concretely, this invention is not restrict | limited at all by these Examples.

  The compounds used in Examples and Comparative Examples, their abbreviations, and methods for evaluating the prepared filling and restorative materials are shown below.

[Radically polymerizable monomer]
Bis-GMA; 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane D-2.6E; 2,2-bis (4- (methacryloyloxyethoxy) phenyl) propane 3G; Triethylene glycol dimethacrylate UDMA; 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane

[Fluorine group-containing radical polymerizable monomer]
5F: 2,2,3,3,4,4-hexafluoro-1,5-pentyl dimethacrylate

[Polymerization initiator]
(Α-diketone)
CQ: camphorquinone (amine compound)
DMBE; p-dimethylaminobenzoic acid ethyl ester

[Filler]
0.3Si-Ti; spherical silica-titania, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (average particle size: 0.3 μm)
0.45 Si—Zr; spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (average particle size: 0.45 μm)

[A dendritic polymer having a fluorine group]
FA-200; hyperbranched polymer particles, manufactured by Nissan Chemical Industries, Ltd., mass average molecular weight 18000. Hydrodynamic mean diameter 7.0 nm. Contact angle for CH ₂ I ₂ (23 ° C.) 77 °, contact angle for water (23 ° C.) 105 °, refractive index (25 ° C.) 1.451

[Dendritic polymer without fluorine group]
HA-DMA-200: hyperbranched polymer particles, Nissan Chemical Industries, Ltd., weight average molecular weight 22000, hydrodynamic mean diameter 5.2 nm, the contact angle with respect to _{CH 2 I 2 (23 ℃)} 31 °, the contact angle with water (23 ° C. ) 70 °, refractive index (25 ° C.) 1.510

Next, in each of the examples and comparative examples, the physical properties of the dental filling / restoration material were evaluated according to the following methods.

(1) Evaluation of gap between tooth and filling restorative material on restoration tooth surface layer A circular cavity having a diameter of about 8 mm and a depth of about 1 mm was formed on the labial surface of the bovine front teeth using a dental diamond point. A dental adhesive (bond force, manufactured by Tokuyama Dental Co., Ltd.) was used to fill the dental filling restorative material, and a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm) ^{In 2} ), light irradiation was performed for 30 seconds to cure the dental filling restorative material. The prepared sample was cut perpendicularly to the tooth surface, and two surface layer edge portions at the boundary between the tooth surface and the filler were observed at a magnification of 50 times using a laser microscope. Observation was performed with four samples, and the above-mentioned surface layer edges were observed in a total of eight locations. A gap between the teeth and the filling restorative material is observed where 6 or more gaps are observed, x is observed when 4 to 5 spots are observed, Δ is observed when 2-3 spots are observed, and a gap is observed. Those which were not observed or were observed only at one place were marked with ◎.

(2) Evaluation of water repellency of dental filling and restoration material Dental restoration material was filled in a 0.5 mm thick polyacetal mold with a 8 mm diameter through-hole, pressed with a polypropylene film, and irradiated with dental light. The test piece was produced by irradiating light for 30 seconds with a container (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ). In a thermostatic chamber at 23 ° C., 1 μL of a water droplet was dropped on the surface of the obtained cured body, and the contact angle was measured.

(3) Measurement of polymerization shrinkage rate A stainless steel (SUS) split mold with a thickness of 7 mm, in which a through hole with a diameter of 3 mm was formed, was inserted with a SUS plunger with a diameter of less than 3 mm and a height of 4 mm in a slightly loose fit state. After filling, one opening of the through hole was closed, and the depth of the hole was adjusted to 3 mm. Next, after filling the hole with a dental filling and restorative material, the upper end of the hole was pressed with a polypropylene film. Next, a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Corp .; light output density 700 mW / cm ² ) was provided below the center of the glass top plate of the glass table. The above-mentioned SUS split mold was placed on the top surface of the glass top plate of the glass table with the surface on which the polypropylene film was attached facing downward. Further, a short needle capable of measuring the movement of a minute needle was brought into contact with the upper surface of the SUS plunger. In this state, the dental filling / restoration material was polymerized and cured by a dental irradiator, and the shrinkage rate [%] 3 minutes after the start of irradiation was calculated from the moving distance of the short needle in the vertical direction.

Examples 1-9, Comparative Examples 1-7
The polymerizable composition was mixed to prepare a matrix composition composed of the following AC.
<Matrix composition A>
D-2.6E: 70 parts by mass 3G: 20 parts by mass UDMA: 10 parts by mass

<Matrix composition B>
-Bis-GMA: 60 mass parts-3G: 40 mass parts

<Matrix composition C>
-5F: 50 mass parts-D-2.6E: 40 mass parts-UDMA: 10 mass parts

Moreover, as the filler composition A, a mixture of 70 parts by mass of 0.3Si-Ti and 30 parts by mass of 0.3Si-Ti was prepared.

  The matrix compositions A to C, the filler composition A, and CQ and DMBE as the polymerization initiator were mixed in the blending amounts shown in Tables 1 and 2 to produce dental filling restorative materials. For these dental filling restoration materials, "Evaluation of gap between teeth and filling restoration material on the surface of restoration tooth", "Water repellency evaluation of dental filling restoration material" and "Measurement of polymerization shrinkage ratio" were carried out. The results are also shown in Table 3.

  As described above, the filling restoration material of each Example containing a dendritic polymer having a fluorine group is a filling restoration material not containing a dendritic polymer or a dendritic shape having no fluorine group of each comparative example. Compared to a filling restorative material containing a polymer, it is difficult to form a gap between the tooth and the filling restorative material on the surface of the restorative tooth, and the water contact angle is high. there were.

Claims (4)

(A) a polymerizable monomer, dendrite with (B) dendritic polymer having a fluorine group, Ri Na contain (C) a polymerization initiator, and (D) a filler, and (B) the fluorine group The macromolecular polymer has a hydrodynamic average diameter in tetrahydrofuran of 1 to 40 nm and a mass average molecular weight of 5,000 to 50,000 as measured by a dynamic light scattering method, and a contact angle with respect to CH ₂ I ₂ (23 ° C. ) Is 60 ° to 130 °, and the dental filling restoration material has a contact angle with water (23 ° C.) of 80 ° to 130 ° . The dental filling / restoration material according to claim 1, wherein the dendritic polymer having a fluorine group has a refractive index (25 ° C.) of 1.4 to 1.7. The dental filling restorative material according to claim 1 or 2 , wherein the blending amount of the (B) dendritic polymer having a fluorine group is 8 to 40 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer. . (D) The compounding quantity of a filler is 70-600 mass parts with respect to 100 mass parts of (A) polymeric monomers, The dental filling restoration material of any one of Claims 1-3 .