JP5153100B2 - Dental restoration material - Google Patents

Description

  The present invention relates to a dental restorative material. More specifically, the present invention relates to a dental restorative material that can be used for bleached teeth and the like by adding a white pigment, in which coloring derived from a polymerization initiator and other components is not conspicuous.

  Dental restoration materials have been increasingly used in dental treatment due to recent development and improvement of adhesive monomers for teeth.

  On the other hand, the consciousness of the patient receiving the repair treatment has also changed, and the conventional treatment of “if it does not hurt, it is ok” has changed to a treatment that seeks “same as or better than before treatment”. Being beautiful also applies to the shape and gloss, but is more pronounced in its color. In other words, from the restoration that focuses on reproducing the color tone close to the conventional natural tooth and the color tone close to the adjacent tooth, there has been a demand for a restoration that requires more whiteness even if it is somewhat unnatural. Against this background, the dental restorative materials are less colored than before, and white materials have been demanded.

  There are various reasons for coloring dental materials. For example, coloring of dyes used as photopolymerization initiators, coloring derived from peroxides / amines used as chemical polymerization initiators, coloring of ultraviolet absorbers, polymerization inhibitors Coloring derived from the above, coloring by trace impurities present in the polymerizable monomer, coloring of the filler, and the like. Among these, coloring due to impurities can be reduced by refining the raw material, but coloring due to a polymerization initiator, an ultraviolet absorber, or a polymerization inhibitor cannot be prevented. In particular, when the polymerization initiator is a visible light curable polymerization initiator containing an α-diketone such as camphorquinone, and the curable composition constituting the dental restorative material is a photocurable composition. In such cases, such coloring was prominent and reduced its commercial value.

  In addition, immediately after the production of the curable composition constituting the dental restorative material, even when the above coloring does not occur, the storage period and the use period as a restorative material after curing are long. When it reaches, it often becomes gradually colored due to deterioration, and in that case, it is also not aesthetically satisfactory.

  In general, these colorings are yellow to orange, and the color intensity is often about -1 to 7 in b * evaluated by a color difference meter at the stage of the curable composition (in this case) The b * of the cured product is about -2 to 5), and it is not acceptable for patients who strongly demand aesthetics to yellow to this extent. Since the dental restorative materials are often used in colors close to natural teeth as described above, pigments have been used for this purpose in order to adjust to the same color tone as natural teeth (for example, Non-Patent Document 1). . In the past, in many cases, it was possible to make the above-mentioned coloring inconspicuous by adding a pigment, but in response to the change in consciousness on the patient side, when trying to adjust a whiter material, the pigment Therefore, the above yellow to orange coloration is conspicuous.

  One method for solving this problem is to add a large amount of white pigment. However, according to this method, the transparency of the dental restorative material is remarkably lowered, resulting in an unnatural color tone. In addition, when applied to a photopolymerizable material, the curing depth becomes small, and it does not function as a restoration material.

  Moreover, the method of making the yellowishness of a filler inconspicuous by adding a fluorescent whitening agent to an organic inorganic composite filler has also been used (for example, Patent Document 1). In this method, the yellowing becomes inconspicuous due to the action of the fluorescent brightening agent when exposed to light, but the effect is small in the dark and it is difficult to say that the effect is sufficiently exhibited in the oral cavity.

Edited by Jiro Hasegawa “Latest Dental Materials and Technologies / Equipment” CMC Corporation p16 Japanese Patent Laid-Open No. 2002-255772

  Therefore, the problem to be solved by the present invention is to satisfy the whiteness required for a dental restorative material, without changing the transparency of the material, making the yellow-orange color derived from raw materials and impurities inconspicuous, It is to provide a dental restoration material that satisfies high aesthetics.

  The present inventors have intensively studied to solve the above problems. As a result, by adding a blue dye and imparting a light blue tint to the material, the present invention has found a dental restorative material composition that does not stand out from yellow to orange without changing the transparency of the material and is aesthetically pleasing. It came to complete.

That is, the present invention, (A) a polymerizable monomer, a (B) visible light curable polymerization initiator comprising α- diketone as a polymerization initiator, and (C) a photocurable composition comprising a filler A dental restorative material comprising (D) 0.01 to 1 ppm of a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm.

The dental restorative material of the present invention, in a curable composition that is colored yellow to orange, (D) the coloring is conspicuous by appropriate bluing with a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm. To lose. In particular, the polymerization initiator is remarkably generated at a visible light curable polymerization initiator comprising α-diketo emissions such as camphorquinone, with respect to the yellowing, good relax the reduction of the aesthetic it can. Moreover, even when the storage period of the curable composition constituting the dental restorative material and the period of use as a restorative material after curing are extended for a long time, due to the occurrence of coloring from yellow to orange due to deterioration It is possible to satisfactorily suppress a decrease in aesthetics. And the moderate transparency requested | required as a dental restoration material is hold | maintained favorably.

  For this reason, according to the dental restorative material of the present invention, it is possible to satisfy a high aesthetic requirement of a patient who desires white teeth, and its industrial value is extremely high.

  The first component used in the dental restorative material of the present invention is (A) a polymerizable monomer. As the polymerizable monomer, known polymerizable monomers are used without limitation, but radically polymerizable monomers and cationically polymerizable monomers are preferably used.

  As the radically polymerizable monomer, a (meth) acrylate polymerizable monomer having no acidic group (sulfonic acid group, carboxyl group, phosphoric acid residue, etc.) is used for curing speed and mechanical properties of the cured product. In addition to physical properties, water resistance, etc., the present invention is preferably used because it is less likely to cause coloring problems for the purpose of improvement.

  The radical polymerizable monomer is preferably a polyfunctional (meth) acrylate polymerizable monomer having a plurality of polymerizable functional groups. As the polyfunctional (meth) acrylate polymerizable monomer, known ones can be used without particular limitation. Examples of those generally used preferably include those shown in the following (I) to (III).

(I) Bifunctional polymerizable monomer (i) Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxy Phenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (hereinafter referred to as D-2. 6E), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxy) Phenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propyl Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) 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; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and diisocyanates Diaducts obtained from addition with a diisocyanate compound having an aromatic group such as methylbenzene and 4,4′-diphenylmethane diisocyanate.

(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.

(II) Trifunctional polymerizable monomer Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.
(III) 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 polyfunctional (meth) acrylate polymerizable monomers may be used in combination of a plurality of types as required.

  Further, if necessary, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. A polymerizable monomer other than the above-mentioned (meth) acrylate monomer may be used. In order to obtain good cured product properties (mechanical strength, non-eluting properties, etc.) as a dental restoration material, the blending amount of monomers other than these polyfunctional (meth) acrylate monomers is The content of the radical polymerizable monomer is 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less.

  On the other hand, when the polymerizable monomer is a cationic polymerizable monomer, any known monomer that can be polymerized by Bronsted acid or Lewis acid is used without any limitation.

  Examples of typical cationic polymerizable monomers include vinyl ether compounds, cyclic ether compounds such as epoxy, oxetane, tetrahydrofuran and oxepane, bicyclic orthoester compounds such as bicycloorthoester and spiroorthoester, spiroorthocarbonate, cyclic Cyclic acetal compounds such as carbonate, 1,3,5-trioxane, 1,3-dioxolane, oxepane, 1,3-dioxepane, 4-methyl-1,3-dioxepane, 1,3,6-trioxacyclooctane, 2,6-dioxabicyclo [2.2.1] heptane, 2,7-dioxabicyclo [2.2.1] heptane, 6,8-dioxabicyclo [3.2.1] octane, etc. Cyclic acetal compounds are mentioned, but they are readily available and volume shrinkage, especially when considering dental applications Small, in terms polymerization reaction faster, oxetane compounds and the epoxy compound is preferably used among others.

  Specific examples of the oxetane compound include trimethylene oxide, 3-methyl-3-oxetanylmethanol, 3-ethyl-3-oxetanylmethanol, 3-ethyl-3-phenoxymethyloxetane, 3,3-diethyloxetane, Those having one oxetane ring such as 3-ethyl-3- (2-ethylhexyloxy) oxetane, 1,4-bis (3-ethyl-3-oxetanylmethyloxy) benzene, 4,4′-bis (3 -Ethyl-3-oxetanylmethyloxy) biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethyloxymethyl) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, bi (3-ethyl-3-oxetanylmethyl) Jifenoeto, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, or a compound shown below

And compounds having two or more oxetane rings.

  In particular, those having two or more oxetane rings in one monomer molecule are preferably used from the viewpoint of physical properties of the obtained cured product.

  The epoxy compound is not particularly limited as long as it is a compound capable of cationic polymerization, and known compounds can be used. Specific examples of the epoxy compound include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxy. Octane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, butadiene monooxide, 2-methyl-2-vinyloxirane, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, epichlorohydrin, epibromohydrin, glycidol, 2-methylglycidol, methylglydidi Ether, ethyl glycidyl ether, glycidyl propyl ether, butyl glycidyl ether , 2-ethylhexyl glycidyl ether, cyclooctene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecane epoxide, exo-2,3-epoxynorbornene, 4-vinyl-1-cyclohexene-1,2-epoxide, limonene oxide, styrene Oxide, (2,3-epoxypropyl) benzene, phenyl glycidyl ether, benzyl glycidyl ether, glycidyl 2-methylphenyl ether, 4-tert-butylphenyl glycidyl ether, 4-chlorophenyl glycidyl ether, glycidyl 4-methoxyphenyl ether, etc. One having an epoxy functional group, 1,3-butadiene dioxide, 1,2,7,8-diepoxyoctane, ethylene glycol jig Sidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 , 5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanemethanol diglycidyl ether, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, diglycidyl suberate, di Glycidyl azelate, diglycidyl sebacate, 2,2-bis [4-glycidyloxyphenyl] propane, 2,2-bis [4-glycidyloxyphe Nyl] hexafluoropropane, 4-vinyl-1-cyclohexene diepoxide, limonene diepoxide, 1,2,5,6-diepoxycyclooctane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Bis (3,4-epoxycyclohexylmethyl) glutarate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) pimelate, bis (3,4-epoxycyclohexylmethyl) suberate, bis ( 3,4-epoxycyclohexylmethyl) zelate, bis (3,4-epoxycyclohexylmethyl) sebacate, 1,4-bis (3,4-epoxycyclohexylmethyloxymethyl) benzene, 1,4-bis (3,4) Epoxy (Rohexylmethyloxymethyl) biphenyl, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, bis (3,4-epoxycyclohexyl) sulfone, methylbis [2- ( 7-oxabicyclo [4.1.0] hept-3-yl) ethyl] phenylsilane, dimethylbis [(7-oxabicyclo [4.1.0] hept-3-yl) methyl] silane, methyl [( 7-oxabicyclo [4.1.0] hept-3-yl) methyl] [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl] silane, 1,4-phenylenebis [Dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl]] silane, 1,2-ethylenebis [dimethyl [2- (7-oxa Cyclo [4.1.0] hept-3-yl) ethyl]] silane, dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl] silane, 1,3-bis [2- (7-Oxabicyclo [4.1.0] hept-3-yl) ethyl] -1,1,3,3-tetramethyldisiloxane, 2,5-bicyclo [2.2.1] heptylene bis [Dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl]] silane, 1,6-hexylenebis [dimethyl [2- (7-oxabicyclo [4.1. 0] hept-3-yl) ethyl]] silane having two epoxy functional groups, or glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, Pentaerythritol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, and

And those having three or more epoxy functional groups. These epoxy compounds may be used in combination.

  In particular, those having two or more epoxy functional groups in one molecule are suitably used from the viewpoint of physical properties of the obtained cured product.

  These cationic polymerizable monomers can be used alone or in combination of two or more. In particular, when A mole of an oxetane compound having an oxetane functional group having an average of 1 molecule per molecule and B mole of an epoxy compound having an epoxy functional group having an average of b molecules per molecule are used (a × A) : (B × B) prepared so as to be in the range of 90:10 to 45:55 is preferable in that the curing rate is high and the polymerization is not easily inhibited by moisture.

The second component of the dental restorative material of the present invention is (B) a polymerization initiator. As the polymerization initiator , a visible light curable polymerization initiator containing an α-diketone can be used . As a polymerization initiator used in the dental field, as a radical polymerization initiator for polymerizing and curing a radical polymerizable monomer, a chemical polymerization initiator (room temperature redox initiator), a photopolymerization initiator, a thermal polymerization initiator, etc. However, in consideration of curing in the oral cavity, a chemical polymerization initiator and / or a photopolymerization initiator is preferable. Moreover, as a cationic polymerization initiator for polymerizing and curing the cationic polymerizable monomer, it is preferable to employ a so-called photoacid generator that generates a Lewis acid or a Bronsted acid by light irradiation.

  Photopolymerization initiators 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, diaryl ketones such as benzophenone, anthraquinone and thioxanthone, diacetyl , Benzyl, camphorquinone, α-diketones such as 9,10-phenanthraquinone, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5- Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxa , Bis (2,4,6-trimethylbenzoyl) - bisacylphosphine oxides such as triphenylphosphine oxide, and the like can be used.

  In addition, a reducing compound is often added to the photo radical polymerization initiator. Examples thereof include 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, dimethylamino. Examples thereof include tertiary amines such as benzaldehyde and terephthalaldehyde, sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid and thiobenzoic acid, and N-phenylalanine.

  As the thermal polymerization initiator, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydicarbonate, diisopropylperoxydicarbonate, An azo compound such as azobisisobutyronitrile can be used.

  Examples of the chemical polymerization initiator include combinations of the above-described peroxides and tertiary amines exemplified as the reducing agent.

  Examples of the photoacid generator include diazonium salt compounds, iron-arene complex salt compounds, diaryliodonium salt compounds, sulfonium salt compounds, pyridinium salt compounds, sulfonic acid ester compounds, and halomethyl-substituted S-. And triazine derivatives.

  Among these, diaryliodonium salt compounds and sulfonium salt compounds are excellent in that the polymerization activity is particularly high. Specific examples of diaryl iodonium salt compounds include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl). ) Iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p- Cations such as octyloxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, Examples thereof include diaryl iodonium salt compounds composed of anions such as trafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate.

  Examples of sulfonium salt compounds include dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8- Cations such as dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl-4-phenylthiophenylsulfonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate , Tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexaful Examples thereof include sulfonium salt compounds composed of anions such as orophosphate, hexafluoroarsenate and hexafluoroantimonate.

  The photoacid generator as described above usually has many compounds that do not absorb in the near ultraviolet to visible range, and a special light source is often required to excite the polymerization reaction. Therefore, it is preferable that a compound having absorption in the near ultraviolet to visible region is further added as a sensitizer in addition to the photoacid generator.

  Examples of the compound used as such a sensitizer include acridine dyes, benzoflavine dyes, condensed polycyclic aromatic compounds such as anthracene and perylene, and phenothiazine.

  Among these sensitizers, a condensed polycyclic aromatic compound is preferable in terms of good polymerization activity, and a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to the condensed polycyclic aromatic ring. Condensed polycyclic aromatic compounds having are preferred.

  Specific examples of such condensed polycyclic aromatic compounds having a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to a condensed polycyclic aromatic ring include 1-methylnaphthalene and 1-ethylnaphthalene. 1,4-dimethylnaphthalene, acenaphthene, 1,2,3,4-tetrahydrophenanthrene, 1,2,3,4-tetrahydroanthracene, benzo [f] phthalane, benzo [g] chroman, benzo [g] isochroman, N-methylbenzo [f] indoline, N-methylbenzo [f] isoindoline, phenalene, 4,5-dimethylphenanthrene, 1,8-dimethylphenanthrene, acephenanthrene, 1-methylanthracene, 9-methylanthracene, 9-ethylanthracene , 9-cyclohexylanthracene, 9,10-dimethyl Luanthracene, 9,10-diethylanthracene, 9,10-dicyclohexylanthracene, 9-methoxymethylanthracene, 9- (1-methoxyethyl) anthracene, 9-hexyloxymethylanthracene, 9,10-dimethoxymethylanthracene, 9- Dimethoxymethylanthracene, 9-phenylmethylanthracene, 9- (1-naphthyl) methylanthracene, 9-hydroxymethylanthracene, 9- (1-hydroxyethyl) anthracene, 9,10-dihydroxymethylanthracene, 9-acetoxymethylanthracene 9- (1-acetoxyethyl) anthracene, 9,10-diacetoxymethylanthracene, 9-benzoyloxymethylanthracene, 9,10-dibenzoyloxymethylanthracene, 9 -Ethylthiomethylanthracene, 9- (1-ethylthioethyl) anthracene, 9,10-bis (ethylthiomethyl) anthracene, 9-mercaptomethylanthracene, 9- (1-mercaptoethyl) anthracene, 9,10-bis (Mercaptomethyl) anthracene, 9-ethylthiomethyl-10-methylanthracene, 9-methyl-10-phenylanthracene, 9-methyl-10-vinylanthracene, 9-allylanthracene, 9,10-diallylanthracene, 9-chloro Methyl anthracene, 9-bromomethylanthracene, 9-iodomethylanthracene, 9- (1-chloroethyl) anthracene, 9- (1-bromoethyl) anthracene, 9- (1-iodoethyl) anthracene, 9,10-dichloromethylanthracene 9,10-dibromomethylanthracene, 9,10-diiodomethylanthracene, 9-chloro-10-methylanthracene, 9-chloro-10-ethylanthracene, 9-bromo-10-methylanthracene, 9-bromo-10 -Ethylanthracene, 9-iodo-10-methylanthracene, 9-iodo-10-ethylanthracene, 9-methyl-10-dimethylaminoanthracene, acanthrene, 7,12-dimethylbenz (A) anthracene, 7,12- Dimethoxymethylbenz (a) anthracene, 5,12-dimethylnaphthacene, collanthrene, 3-methylcholanthrene, 7-methylbenzo (A) pyrene, 3,4,9,10-tetramethylperylene, 3,4,9, 10-tetrakis (hydroxymethyl) perylene, bio Nsuren, Isoviolanthrone Ren, 5,12-dimethyl-naphthacene, 6,13-dimethyl pentacene, 8,13- dimethyl penta Fen, 5,16- dimethyl hexamethylene Sen, 9,14- dimethyl hexa Fen and the like.

  Examples of the condensed polycyclic aromatic compound other than the above include naphthalene, phenanthrene, anthracene, naphthacene, benz [a] anthracene, pyrene, perylene and the like.

  Further, in order to further increase the activity of the photopolymerization initiator, it is possible to use the photoacid generator in combination as a photoradical polymerizable initiator. In this case, as the photopolymerization initiator, α-diketones such as camphorquinone are preferable, and a reducing agent such as 4-dimethylaminobenzoic acid is preferably used in combination.

  As described above, the cause of coloring of the dental restorative material is that coloring is caused by the additive when the ultraviolet absorber is used, coloring caused by the polymerization inhibitor, coloring due to a small amount of impurities present in the polymerizable monomer. There are various causes such as coloring of the filler, and among them, those related to the use of the polymerization initiator are particularly significant. That is, coloring of pigments used as photopolymerization initiators, coloring derived from peroxides / amines used as chemical polymerization initiators, etc. Among these, diacetyl, benzyl, camphorquinone, 9,10-phenol When a visible light curable polymerization initiator comprising an α-diketone such as nantraquinone is used, these photopolymerization initiators are dyes strongly colored yellow to orange, and the above-mentioned coloring problem occurs. Since it occurs remarkably, the effect of the present invention is exhibited satisfactorily and is suitable.

  These polymerization initiators may be used alone or in combination of two or more. Moreover, what is necessary is just to select the compounding quantity according to the objective, but it is a ratio of 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable monomers, More preferably, 0.1-5 mass parts Used at a rate of

  The third component of the dental restorative material of the present invention is (C) a filler. The filler is blended from the viewpoints of improving the mechanical strength and reducing the polymerization shrinkage rate in the cured body of the dental restorative material.

  As the filler, known fillers can be used without limitation, and any of inorganic fillers and organic fillers may be used, but usually inorganic fillers are used. Specific examples of such inorganic fillers include spherical particles such as amorphous silica, silica-zirconia, silica-titania, silica-titania-barium oxide, silica-titania-zirconia, quartz, alumina, glass, etc. Mention may be made of shaped particles. Of these, composite oxides mainly composed of silica and zirconia, silica and titania, or silica and barium oxide are preferably used because they have high X-ray contrast properties. In addition, since the filler has a spherical shape, it is particularly preferably used since a cured body of a dental restorative material having particularly excellent wear resistance and surface smoothness can be obtained.

  The inorganic filler may be treated with a surface treatment agent typified by a silane coupling agent in order to improve compatibility with the polymerizable monomer (A) and improve mechanical strength and water resistance. desirable. The surface treatment may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltris (2-methoxyethoxy) silane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxy Chlohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 3-ethyl-3- [3- (triethoxysilyl) propoxymethyl] oxetane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyl Disilazane and the like are preferably used. The said silane coupling agent should just be selected suitably according to a polymerizable monomer, and can use it combining 1 type or 2 types or more.

  Furthermore, the above-mentioned inorganic filler can be used as a filler (hereinafter also referred to as an organic-inorganic composite filler) which is previously mixed with a polymerizable organic matrix, cured and pulverized. The particle size of the organic-inorganic composite filler is about 1 μm to 100 μm, and the particle size does not directly affect the surface glossiness of the composite resin. However, when the particle size is large, the paste is rough and affects operability. For this reason, Preferably it is 3-70 micrometers, More preferably, it is 5-50 micrometers.

  The polymerizable organic matrix used for the organic-inorganic composite filler is not particularly limited, and a known polymerizable organic matrix is used. If the polymerizable organic matrix used suitably is illustrated, the mixture of the polymerizable monomer of this invention and a polymerization initiator can be mentioned.

  In the present invention, the blending amount of the filler may be selected according to the purpose, but is usually a ratio of 100 to 1000 parts by mass, more preferably 110 to 900 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Used at a rate of

The greatest feature of the present invention, these polymerizable monomer (A), (B) visible light curable polymerization initiator comprising α- diketone as a polymerization initiator, and (C) photocuring containing filler The dental restorative material composed of the curable composition comprises (D) 0.01 to 1 ppm of a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm with respect to the entire curable composition. . That is, a dental restorative material composed of such a curable composition is colored yellow to orange for the various reasons described above, and is often in a state where the aesthetics of the cured product cannot be sufficiently satisfied. This yellowing often occurs gradually even during the storage period of the adhesive composition or when the period of use as a restoration material after curing is extended for a long time. In the present invention, in contrast to coloring of the curable composition, a small amount of the blue dye having the maximum absorption wavelength is added to the composition as described above, so that the blue color is lightly colored, and this yellowing occurs. However, the reflection spectrum is made as uniform as possible to make it inconspicuous.

Here, when the maximum absorption wavelength of the blue dye is less than 575 nm, red is conspicuous, and when the maximum absorption wavelength exceeds 680 nm, green is conspicuous. With these colors, the above yellow to orange coloring is sufficiently inconspicuous. It will not be done. For this reason, the maximum absorption wavelength of the blue dye is in the range of 610 to 650 nm.

  Further, it is important that the blue color material having the maximum absorption wavelength is a dye. Here, the dye is dissolved in the polymerizable monomer (A) and uniformly mixed in the curable composition. Thus, since blue dye is uniformly mixed with respect to a curable composition, it is thought that the effect which makes yellow-orange coloring inconspicuous is high. Further, since the blue dye is uniformly dissolved in the curable composition, the transparency of the dental restoration material is not impaired. For this reason, it is possible to maintain translucency similar to that of a tooth, and when a white pigment is added, it is possible to adjust the color tone applicable to bleached teeth. Even if the same blue color material is used, the pigment of the color is not mixed uniformly, the effect of canceling the yellow-orange coloring is not sufficient, and further the transparency of the curable composition is lowered. It will also be a thing.

  Content of the said blue dye to a curable composition is 0.01-1 ppm. If it exceeds 1 ppm, the blue color of the dye becomes conspicuous, and if it is less than 0.01 ppm, the effect of making the coloring inconspicuous does not appear. For this reason, the content of the blue dye is 0.01 to 1 ppm, preferably 0.03 to 0.7 ppm, and most preferably 0.05 to 0.5 ppm.

  In addition, by including a blue dye in such an amount, b * evaluated by a color difference meter of the curable composition is usually usually -10 to 1 at the beginning of the production of the curable composition. More preferably, it is −9 to 0 (in this case, the b * of the cured product of the curable composition is usually −12 to −1, and −10 to −2). Some are more preferred).

In the present invention, the curable composition in which the blue dye is blended is one in which b * evaluated with a color difference meter is yellowed to -1 to 7, more preferably 0 to 5 in a state where the blue dye is not blended. The effect of making the coloring due to the combination of the blue dye inconspicuous is particularly noticeable and preferable. The curable composition yellowed in this way, which is mixed with the blue dye, is usually prepared at the time of production in which the respective components are mixed. In this case, the blue dye is mixed with the respective components. These components may be mixed together in any combination order. Further, if the yellowing curable composition is yellowed to the above degree due to deterioration during storage, the blue dye may be added to the curable composition after storage. . That is, according to the present invention, the curable composition comprising (A) a polymerizable monomer, (B) a polymerization initiator, and (C) a filler, and b * evaluated by a color difference meter is −1 to 7. There is also provided a method for producing the dental restorative material, wherein (D) 0.01 to 1 ppm of a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm is contained in the product.

  On the other hand, if the present invention is applied even to a curable composition that is not colored in this way, it will deteriorate in subsequent storage of the curable composition and further in use as a restoration material after curing. When coloring due to is generated, this coloring is favorably relaxed and aesthetics can be maintained, which is preferable.

  In the present invention, the maximum absorption wavelength of the blue dye is measured using toluene as a solvent and at a dye concentration such that the absorbance at the maximum absorption wavelength is in the range of 0.3 to 0.8.

As the blue dye used in the present invention, a known blue dye can be used as long as the maximum absorption wavelength is in the range of 610 to 650 nm. In general, an anthraquinone derivative is preferable. The blue dyes that are preferably used are indicated by specific trade names, such as Dial Resin Blue J, Dial Resin Blue K, Dial Resin Blue P, Dial Resin Blue G, Dial Resin Blue N, Dial Resin Blue 4G, dialresin blue H3G, dialresin blue LR and the like. Among these, Dialresin Blue LR, Dialresin Blue P, and Dialresin Blue K are preferable. These blue dyes may be used alone or in combination of two or more.

  In the present invention, other dyes, pigments, and fluorescent pigments may be added as long as the effect of blending the blue dye is not impaired. Among these, a white pigment can be suitably contained with respect to the dental restoration material used for a bleached tooth. As the white pigment, known pigments are used without limitation, and specific examples include titanium dioxide, alumina, zirconia, and zinc oxide, with titanium dioxide being preferred.

  The white pigment may be added in an amount that does not impair the effects of the present invention, but is generally 0.01 to 1% by mass, preferably 0.02 to 0.5% by mass.

  Furthermore, you may mix | blend other additives, such as a polymerization inhibitor and a ultraviolet absorber, with the dental restorative material of this invention in the range which does not affect an effect as needed.

In the case of producing a curable composition by mixing the components described above, the blending order is not particularly limited, and may be carried out in any order. That is, for the polymerizable monomer (A), (B) visible light curable polymerization initiator comprising α- diketone as a polymerization initiator, and (C) a photocurable composition comprising a filler, (D) Not only a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm may be blended, but these components may be added and mixed simultaneously, and these components may be blended in any order. May be. (A) a polymerizable monomer, (B) a polymerization initiator, and (D) a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm are mixed first, and (C) In general, a filler is added and mixed well in a mortar to obtain a uniform paste.

  The curable composition containing the blue dye is used as a dental restoration material. Here, examples of the dental restorative materials include dental filling restorative materials such as composite resins; dental cements; indirect restorative materials for inlays, onlays, crowns and bridges; and materials for restoring denture bases. It is done. Among these, in particular, it can be suitably used for dental filling restoration materials such as composite resins and indirect restoration materials for dental crowns.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the abbreviations of the compounds used in the following Examples and Comparative Examples are shown below.
(1) Abbreviations / abbreviations (A) Polymerizable monomer / GMA: 2,2-bis [(3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane / D2.6E: 2,2-bis (4 -(Methacryloyloxypolyethoxyphenyl) propane, 3G: triethylene glycol dimethacrylate, UDMA: 1,6-bis (methacrylethyloxycarbonylamino) trimethyloxane, HD: hexamethylenediol dimethacrylate (B) polymerization initiator, CQ: camphorquinone, DMBE: ethyl 4-dimethylaminobenzoate, MDA: N-methyldiethanolamine, TCT: 2,4,6-tris (trichloromethyl) -s-triazine (C) blue dye, PBP: dialresin, blue P Maximum absorption wavelength 644nm
・ PBK: Dialresin ・ Blue K Maximum absorption wavelength 646nm
(D) Filler F-1: Spherical silica-zirconia with an average particle size of 0.4 μm F-2: Spherical silica-titania with an average particle size of 0.08 μm F-3: Spherical with an average particle size of 0.2 μm Silica-zirconia, F-4: Spherical silica-zirconia having an average particle diameter of 0.2 μm and organic / inorganic composite filler having an average particle diameter of 40 μm composed of 3G / GMA / HD = 25/35/40 Other components PB60: Blue pigment Pigment Blue 60
Moreover, the following methods were used for the preparation method of a dental restoration material, the color tone and transparency of a hardened body, the evaluation of yellowishness, and the measurement of light resistance.

(1) Color tone of hardened body The paste-like curable composition was filled in a tetrafluoroethylene mold having a diameter of 7 mm and a thickness of 1 mm and irradiated with light in a state of being pressed by a polypropylene film to obtain a hardened body. The color tone of this cured product was measured using a color difference meter (TC-1500MK-II, manufactured by Tokyo Denshoku Co., Ltd.) with a standard black plate placed on the back side of the sample, and the color tone (L *, a *, b *) was measured. . Yellowness was evaluated by b *.

(2) Transparency of cured body The Y value which is one of the tristimulus values was measured using the same cured body and color difference meter as in (1). At this time, Y. According to the method shown in Miyagawa et al., “Journal of Rental Research”, 60 (5), 890-894, 1981, a standard white plate (X = 81.2, Y = 82.7, Z = 93) .8) and Y value (hereinafter referred to as Yw) when a standard black plate (X = 0.1, Y = 0.1, Z = 0.2) is placed on the back side of the sample. The Y value (hereinafter referred to as Yb) was measured, and the contrast ratio indicating the opacity of the cured product was calculated by the following equation.

Contrast ratio = Yb / Yw
The transparency was calculated by the following formula using the contrast ratio.

Transparency = 1−Contrast ratio = 1−Yb / Yw
The transparency varies in the range from 0 to 1, and the larger the value, the higher the transparency.

(3) Evaluation of coloring (yellowishness) by visual observation The same cured product as in (1) was observed on a standard white plate and evaluated according to the following criteria.

  ○: The yellowish color is hardly noticeable.

  (Triangle | delta): Yellow, blue, green, or purple taste is somewhat conspicuous.

  X: Yellow, blue, green, or purple taste is conspicuous.

(4) Evaluation of light resistance Using a fade meter equipped with a xenon lamp (xenon weather meter X25, Suga Test Instruments Co., Ltd.), the cured product of (3) was exposed to light for 10 hours to determine the degree of coloring ( Evaluation was performed in the same manner as in 3).

Example 1
Since the amount of blue dye added is very small, a master batch of about 0.1% by weight (1000 ppm) of blue dye diluted with a polymerizable monomer is prepared in advance, and a small amount of blue dye is used with this. Weighed accurately.

A master batch of 1000 ppm was prepared by adding 0.01 parts by weight of blue dye PBP to GMA (6 parts by weight) and 3G (4 parts by weight). Under a red lamp, with respect to 100 parts by mass of a polymerizable monomer composed of GMA (60 parts by mass) and 3G (40 parts by mass), 0.055 parts by mass of a master batch and 0 hydroquinone monomethyl ether as a polymerization inhibitor .15 parts by mass and 0.20 parts by mass of CQ as a photopolymerization initiator, 0.28 parts by mass of DMBE, 0.12 parts by mass of MDA and 0.16 parts by mass of TCT may be mixed and stirred uniformly. A solution was obtained. As a filler, 182 parts by mass of F-3 and 274 parts by mass of F-4 were added, and 0.20 part by mass of titanium dioxide was further added as a white pigment. The PBP at this time was 0.1 ppm with respect to the dental restorative material. These were mixed and stirred well in an agate mortar until a uniform paste was formed. Further, this was vacuum degassed to obtain a paste of a dental restorative material having a predetermined composition. Table 2 shows the results of measuring various physical properties of the obtained dental restorative material.
Examples 2-4, Comparative Examples 1-3
In Examples 2 to 4 and Comparative Examples 1 to 3, the same polymerization inhibitor and photopolymerization initiator as in Example 1 were used in the same parts by mass, and the other components were used in the composition shown in Table 1 for dental use. A restoration material was prepared and carried out. Table 2 shows the results of measuring various physical properties of the obtained dental restorative material.

Claims (3)

Polymerizable monomer (A), (B) visible light curable polymerization initiator comprising α- diketone as a polymerization initiator, and (C) a dental restorative material comprising a photocurable composition comprising a filler And (D) a dental restorative material containing 0.01 to 1 ppm of a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm. The dental restorative material according to claim 1, wherein the photocurable composition contains 0.01 to 1% by mass of a white pigment. ( A) a polymerizable monomer, (B) a visible light curable polymerization initiator comprising an α-diketone as a polymerization initiator, and (C) a filler, and b * evaluated by a color difference meter is −1. The dental restorative material according to claim 1, wherein (D) a blue dye having a maximum absorption wavelength in the range of 610 to 650 nm is contained in the photocurable composition of ˜7. Manufacturing method.