WO2019131881A1 - Résine composite dentaire autocollante - Google Patents

Résine composite dentaire autocollante Download PDF

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Publication number
WO2019131881A1
WO2019131881A1 PCT/JP2018/048143 JP2018048143W WO2019131881A1 WO 2019131881 A1 WO2019131881 A1 WO 2019131881A1 JP 2018048143 W JP2018048143 W JP 2018048143W WO 2019131881 A1 WO2019131881 A1 WO 2019131881A1
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group
meth
polymerizable monomer
filler
mass
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PCT/JP2018/048143
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English (en)
Japanese (ja)
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周明 石原
雄輝 大山
康雄 平田
誉也 小柳
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クラレノリタケデンタル株式会社
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Priority to JP2019562167A priority Critical patent/JP7183185B2/ja
Publication of WO2019131881A1 publication Critical patent/WO2019131881A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon

Definitions

  • the present invention relates to a self-adhesive dental composite resin. More specifically, the present invention relates to a self-adhesive dental composite resin which has a high surface hardness, a good dischargeability from a container, an appropriately suppressed flowability of a paste, and a resistance to dripping when applied to the oral cavity.
  • restoration with a dental adhesive and a dental composite resin has been generally performed.
  • repair treatment work is performed in the following procedure. First, a cavity is formed by scraping a carious portion, and then a dental adhesive is applied to the cavity, and then the site to which the adhesive is applied is irradiated with visible light to be cured. Next, the dental composite resin is filled on the cured adhesive layer, and the final filled dental composite resin is irradiated with visible light to be cured.
  • the self-adhesive dental composite resin comprises teeth, in addition to the components of the conventional dental composite resin of a multifunctional polymerizable monomer and filler for imparting mechanical strength, and a polymerization initiator for improving the hardenability
  • polymerizable monomers having an acidic group conventionally used in dental adhesives are contained as components (for example, Patent Documents 1 and 2).
  • (meth) acrylate As a polymerizable monomer mixed in a dental composite resin, (meth) acrylate is generally used.
  • (meth) acrylate is generally used.
  • imparting of self-adhesiveness and adhesion strength to tooth substance are made.
  • a polymerizable monomer having an acidic group such as a phosphoric acid group or a carboxy group is blended.
  • Patent Document 2 a filler having a low reactivity with an acidic component, for example, a silica filler treated with a silane coupling agent, as a filler to be blended in a self-adhesive dental composite resin.
  • JP 2008-260752 A JP-A-2015-507610
  • Self-adhesive dental composite resin is compatible with having the dischargeability that can be filled directly into the cavity from the storage container such as a syringe, while providing the sagging property that the paste does not drip when applied to the oral cavity. It was difficult.
  • the present invention includes visible light as well as conventional dental composite resin, by including a multifunctional polymerizable monomer, a filler, and a polymerization initiator, and containing a specific surface-treated filler. While having sufficient mechanical strength after polymerization and curing by irradiation, the flowability of the paste is appropriately suppressed, it is difficult to sag even when applied to the oral cavity, and it has self-ejecting property that can be directly filled from the storage container into the cavity An object of the present invention is to provide an adhesive dental composite resin.
  • the present invention includes the following inventions.
  • a self-adhesive dental composite resin comprising 0.1 to 15 parts by mass of the filler (d) based on 100 parts by mass of a total amount of polymerizable monomer components.
  • R 2 is an unsubstituted hydrolyzable group
  • R 3 is an unsubstituted C 1 to C 3 alkyl group
  • R 4 , R 5 and R 6 are each independently hydrogen An atom or unsubstituted C 1 to C 3 alkyl group
  • at least one of R 4 , R 5 , and R 6 is an unsubstituted C 1 to C 3 alkyl group
  • R 7 , R 8 and R 9 is each independently a hydrogen atom or an unsubstituted C 1 to C 3 alkyl group
  • at least one of R 7 , R 8 and R 9 is an unsubstituted C 1 to C 3 alkyl group
  • the silane coupling agent (A) is selected from 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and
  • the self-adhesive dental composite resin according to any one of the above [1] to [3], which is one or more selected from the group consisting of 6-methacryloyloxyhexyl trimethoxysilane.
  • the organosilazane (B) is 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, and 1,1,1,3,
  • [6] 1 to 40 parts by mass of the acidic group-containing (meth) acrylic polymerizable monomer (a) in the total amount of 100 parts by mass of the polymerizable monomer component, and a polyfunctional group not containing the acidic group
  • the photopolymerization initiator (c) is contained in an amount of 30 to 95 parts by mass of the (meth) acrylic polymerizable monomer (b) and 0.001 to 100 parts by mass of the total amount of the polymerizable monomer components.
  • the self-adhesive dental composite according to any one of the above [1] to [5], which contains 20 parts by mass, 0.1 to 10 parts by mass of the filler (d) and 25 to 400 parts by mass of the filler (e) Resin.
  • the content of the multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton is 0.5 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component 7]
  • Self-adhesive dental composite resin is 0.5 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component 7] Self-adhesive dental composite resin.
  • the hydrophilic monofunctional polymerizable monomer (g) is a hydrophilic monofunctional (meth) acrylate type polymerizable monomer and a hydrophilic monofunctional (meth) acrylamide type polymerizable monomer
  • the above-mentioned [9] or [9], wherein the content of the hydrophilic monofunctional polymerizable monomer (g) is 1 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component.
  • Self-adhesive dental composite resin Self-adhesive dental composite resin.
  • the self-adhesive dental composite resin of the present invention while having sufficient mechanical strength after polymerization and curing by visible light irradiation, the flowability of the paste is appropriately suppressed, it is difficult to droop even when applied to the oral cavity, and from the storage container to the cavity
  • a self-adhesive dental composite resin is provided that has direct-to-fill exhalation properties. Moreover, since it has the characteristics that surface hardness is high, it is excellent in abrasion resistance and abradability, and pigment deposition can be suppressed, it can be used suitably for dental composite resin. Furthermore, the self-adhesive dental composite resin of the present invention also has an effect that the change in paste properties is small during long-term storage.
  • FIG. 1 is an explanatory view of a reaction mechanism in the case where the organosilazane (B) according to one embodiment of the present invention is 1,1,1,3,3,3-hexamethyldisilazane.
  • FIG. 2 is explanatory drawing regarding the dispersion state of the filler (e) in a paste, a filler (d), and a filler (e).
  • (meth) acryl is used by the meaning which includes both methacryl and an acryl.
  • the upper limit value and the lower limit value of numerical ranges can be combined as appropriate.
  • the self-adhesive dental composite resin of the present invention has sufficient mechanical strength after polymerization and curing by visible light irradiation, the flowability of the paste is appropriately suppressed, and it is difficult to sag even when applied in the oral cavity, The reason why the change in paste properties is small during long-term storage is not clear, but is estimated as follows.
  • a silanol group (-SiOH) formed by hydrolysis of the alkoxy group of the silane coupling agent (A) and a filler (e)
  • the silanol groups (—SiOH) on the surface of the are chemically bonded by dehydration polycondensation.
  • the silanol group (-SiOH) on the surface of the filler (e) or the silanol group (-SiOH) derived from the silane coupling agent (A) remains as an unreacted material (hereinafter, this remaining silanol group Is called “residual silanol group”.
  • the residual silanol group (-SiOH) can be hydrophobized by the deammonia reaction with (B).
  • the residual silanol group (-SiOH) on the surface of the filler (e) or the residual silanol group (-SiOH) derived from the silane coupling agent (A) on the surface of the filler (e) is as small as possible by the treatment (deammoniating reaction) with this organosilazane (B). It is considered possible.
  • a proton generated from the acidic group-containing (meth) acrylic polymerizable monomer (a), which is an essential component from the viewpoint of imparting adhesiveness to a self-adhesive dental composite resin It is less likely that hydroxyl groups (-OH) or the like contained in (H + ) or other polymerizable monomers cause strong interactions with silanol groups (-SiOH) due to hydrogen bonds, and the filler (e ) Is considered to be highly dispersed, and this highly dispersed state provides the paste with high fluidity.
  • the paste does not intend to treat the gingiva or dentin other than the filling point until it is filled with the cavity and hardened with a visible light irradiator There was a problem of flowing to the place.
  • the filler (e) has an isoelectric point of less than 6.0, is considered to be negatively charged in a paste having a pH equal to or higher than the isoelectric point of the filler (e), and is dispersed by its zeta potential.
  • the filler (d) has a charge opposite to that of the filler (e), ie, positively charged, and the fillers (d) also disperse It is thought that As shown in FIG. 2, when the filler (d) and the filler (e) are simultaneously present in the paste, the filler (d) and the filler (e) form and maintain electrostatically weak association state, As a result, the flowability of the paste is appropriately suppressed, the dripping property of the paste is improved, the change of the paste property is small during long-term storage, and the dischargeability can be directly filled from the storage container into the cavity it is conceivable that.
  • the surface hardness is improved by the blending of the filler (d).
  • the filler (d) and the filler (e) form an electrostatic association state, and the packing density per unit volume of paste is improved by being in a close packing state.
  • the surface hardness increased due to an increase in the amount of filler on the surface of the cured product.
  • the filler (d) having an isoelectric point of 6.0 or more used in the present invention will be described.
  • the isoelectric point of the filler indicates the pH when the zeta potential of the particles in the aqueous dispersion is 0 mV.
  • the zeta potential refers to a value measured by laser Doppler velocimetry.
  • the particles move towards the electrode when an electric field is applied to the aqueous dispersion.
  • the moving speed of the particles is proportional to the charge amount of the particles. Therefore, the zeta potential can be determined by measuring the moving speed of the particles.
  • An aqueous dispersion of particles having an isoelectric point has a zeta potential of 0 mV at a certain pH when the pH is changed. Therefore, the acid or alkali is added to the aqueous dispersion to track the zeta potential while changing the pH continuously, and the obtained measurement data is obtained by plotting the X axis as the pH and the Y axis as the zeta potential. By drawing a line in consideration of the above plot, the pH at which the zeta potential becomes 0 mV can be calculated, and the pH becomes the isoelectric point of the particles.
  • the filler (d) in the present invention as long as the isoelectric point is 6.0 or more, conventionally known materials can be used without any limitation, but metals such as alumina, zirconia, titania, zinc oxide and nickel oxide Composite metal oxides such as oxides, alumina-zirconia, alumina-titania, zirconia-titania and the like can be mentioned. Among them, alumina, zirconia and titania are more preferable, alumina and zirconia are more preferable, and alumina is most preferable. One of these may be used alone, or two or more may be used in combination.
  • the average particle size of the filler (d) is preferably 0.001 to 0.5 ⁇ m, more preferably 0.003 to 0.4 ⁇ m, and still more preferably 0.005 to 0.3 ⁇ m. Within these ranges, the dischargeability from the container is excellent, the flowability is appropriate, the liquid is less likely to sag, and during storage over a long period of time, the change in paste properties is small and the surface hardness is also excellent.
  • the average particle size of the filler means the average particle size (average primary particle size) of the primary particles of the filler.
  • the average particle size of the filler can be determined by particle size distribution measurement or electron microscopic observation.
  • the average particle size is 1.0 ⁇ m or more, it is preferable to use a particle size distribution measuring device, and when the average particle size is less than 1.0 ⁇ m, it is preferable to use electron microscope observation.
  • the particle size distribution can be measured, for example, with a laser diffraction type particle size distribution measuring apparatus (SALD-2100: manufactured by Shimadzu Corporation) using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium.
  • SALD-2100 laser diffraction type particle size distribution measuring apparatus
  • Electron microscopic observation takes, for example, a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) photograph of particles, and the particle diameter of particles (200 or more) observed in the unit field of the photograph is It can obtain
  • the particle diameter of the particles is obtained as an arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter thereof.
  • the content of the filler (d) is at least 0.1 parts by mass with respect to 100 parts by mass of the polymerizable monomer component from the viewpoint of being excellent in appropriate fluidity, sag and surface hardness. It is necessary and preferably 0.2 parts by mass or more, and more preferably 0.3 parts by mass or more from the viewpoint of paste properties such as appropriate fluidity and sag of the self-adhesive dental composite resin. Also, from the viewpoint of not impairing the operability of the paste, such as the adhesive strength of the self-adhesive dental composite resin and the dischargeability from the container, the amount is 15 parts by mass or less based on 100 parts by mass of the total polymerizable monomer component.
  • the amount is 10 parts by mass or less, more preferably 8 parts by mass or less. Therefore, from the above viewpoint, the content of the filler (d) is 0.1 to 15 parts by mass, preferably 0.2 to 10 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable monomer component. 0.3 to 8 parts by mass is more preferable.
  • the filler (d) is preferably treated with a surface treatment agent.
  • the surface treatment agent is selected from the group consisting of an acidic group-containing (meth) acrylic polymerizable monomer (a) described later and / or an organic silicon compound, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound. And at least one organometallic compound.
  • it may be a surface treatment layer of a mixture of two or more kinds of organic metal compounds, or as a surface treatment layer of a multilayer structure in which two or more kinds of organic metal compound layers are laminated. Good.
  • organosilicon compounds examples include compounds represented by (W) n SiY 4-n (wherein W is a C 1 to C 12 substituted or unsubstituted hydrocarbon group, and Y is C an alkoxy group having 1 ⁇ C 4, a hydroxyl group, a halogen atom or a hydrogen atom, n is respectively when there are a plurality of .W and Y is 0, 1, 2 or 3, may be the same or different ).
  • a coupling agent having a functional group copolymerizable with the polymerizable monomer component such as ⁇ - (meth) acryloyloxyalkyltrimethoxysilane (a carbon between a (meth) acryloyloxy group and a silicon atom Number: 3 to 12), ⁇ - (meth) acryloyloxyalkyltriethoxysilane (number of carbons between (meth) acryloyloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and the like are particularly preferably used.
  • ⁇ - (meth) acryloyloxyalkyltrimethoxysilane a carbon between a (meth) acryloyloxy group and a silicon atom Number: 3 to 12
  • organic titanium compound examples include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and the like.
  • organic zirconium compound examples include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconyl acetate and the like.
  • organoaluminum compound examples include aluminum acetylacetonate, and an aluminum organic acid salt chelate compound.
  • the shape of the filler (d) is not particularly limited and may be appropriately selected according to the properties desired to be enhanced as a dental composite resin, and specifically, it can be used as a powder of amorphous or spherical particles .
  • a filler (d) having an isoelectric point of not less than 6.0 is used, a filler (d) having a spherical isoelectric point of not less than 6.0 is particularly excellent in mechanical strength and abrasion resistance. When used, it is particularly excellent in polishing lubricity and lubricity durability.
  • the reactive filler (d) in the present invention commercially available products may be used.
  • the C 1 -C 3 alkyl groups repel each other due to their hydrophobicity. Accordingly, the filler (e) of the present invention is difficult to be aggregated even in the self-adhesive dental composite resin due to the repulsive force of the C 1 to C 3 alkyl groups, and is not easily aggregated even in the powder state.
  • the filler (e) has an isoelectric point of less than 6.0, is treated with a surface treatment agent, and has an average particle diameter of 0.001 to 50.0 ⁇ m, and the surface treatment agent has a general formula (1)
  • the known filler used for the dental composite resin is not limited. used.
  • various kinds of glasses [oxides such as heavy metals, boron, aluminum and the like in the range which contains silica as a main component and has an isoelectric point less than 6.0] contains.
  • glass powder of a general composition such as liquid phase synthetic amorphous silica, fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (Pyrex (registered trademark) glass); barium glass, Dental glass powders such as strontium borosilicate glass, lanthanum glass ceramics, fluoroaluminosilicate glass, etc., composite oxides such as silica-titania and silica-zirconia, calcium fluoride having a core-shell structure surface-coated with silica, silica Fluoride-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium fluoride, silica surface-coated core-shell structure calcium phosphate, silica surface-coated core-shell structure sulfuric acid Barrio , Zirconium dioxide core-shell structure having a surface coated with silica, titanium dioxide coated core-shell structure of the surface with
  • various glasses such as various silicas, complex oxides such as silica-titania and silica-zirconia, and silicas, from the viewpoint of being able to react efficiently with the silane coupling agent (A) or organosilazane (B) -Coated core-shell structure calcium fluoride, silica surface-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium-fluoride, silica surface-coated core-shell structure calcium phosphate , Barium sulfate of core-shell structure coated with silica, zirconium dioxide of core-shell structure coated with silica, titanium dioxide of core-shell structure coated with silica, core-shell structure of silica coated surface Hydroxyapatite Siri Ytterbium fluoride of core-shell structure coated surface in, yttrium fluoride of the core-shell structure coated with silica are preferred.
  • One of these may be used alone,
  • the average particle size of the filler (e) is 0.001 to 50.0 ⁇ m, preferably 0.01 to 50.0 ⁇ m, more preferably 0.03 to 20.0 ⁇ m, and 0.05 to 10.0 ⁇ m. More preferably, 0.05 to 5 ⁇ m is particularly preferable, and 0.05 to 1 ⁇ m is most preferable. Within these ranges, sufficient mechanical strength can be obtained, no stickiness occurs in the paste, no problem occurs in operability, and the abrasion resistance or lubricity durability of the cured product is excellent.
  • the filler (e) used in the present invention is hard to aggregate, it can be easily washed with water. For this reason, the filler (e) used in the present invention is an acid-base reaction with an acidic group-containing (meth) acrylic polymerizable monomer (a), and a content of an ionic impurity such as an alkali metal to be chelated. Can be reduced.
  • the filler (e) is obtained by surface treating the filler (e) with the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2).
  • the hydroxyl group present on the surface of the filler (e) is substituted with a functional group derived from the silane coupling agent (A) Ru.
  • the order of the surface treatment of the filler (e) is not particularly limited.
  • the filler (e) is sequentially surface-treated with the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2).
  • the surface may be treated by adding it at the same time.
  • the filler (e) may first be reacted with the silane coupling agent (A) represented by the general formula (1), and then the organosilazane (B) represented by the general formula (2) may be reacted.
  • the filler (e) is first reacted with the organosilazane (B) represented by the general formula (2), then the silane coupling agent (A) represented by the general formula (1) is reacted, The organosilazane (B) represented by the general formula (2) may be reacted.
  • a method of surface treatment of the filler (e) a method of bonding the silane coupling agent (A) represented by the general formula (1) to the surface of the filler (e) by a dehydration polycondensation reaction, and a general formula (2)
  • the method is not particularly limited as long as it is a method of bonding the organosilazane (B) represented by (IV) to the surface of the filler (e) by a deammonia reaction.
  • the agent is stirred and mixed in a solvent and then heated and dried.
  • the solvent is not particularly limited, and examples thereof include alcohol solvents such as methanol, ethanol and isopropanol, water, and mixed solvents thereof.
  • the heating temperature is not particularly limited, but may be about 30 to 90.degree.
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is a hydrolyzable group which may have a substituent.
  • R 3 is a C 1 to C 3 alkyl group which may have a substituent.
  • p is an integer of 1 to 13, preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.
  • q is 2 or 3, preferably 3.
  • the hydrolyzable group which may have a substituent of R 2 is not particularly limited, and examples of the hydrolyzable group include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- A C 1 to C 6 linear or branched alkoxy group such as butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, isohexyloxy group; A chlorine atom or an isocyanate group is mentioned.
  • the alkoxy group as a hydrolyzable group is a C 1 to C 4 linear alkoxy group, which is any of a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Is more preferable, and a C 1 to C 3 linear alkoxy group is more preferable.
  • the hydrolyzable group of R 2 may be unsubstituted.
  • R 1 is a methyl group
  • R 2 is an unsubstituted C 1 to C 6 linear or branched alkoxy group
  • R 3 Is preferably a substituted C 1 to C 3 alkyl group
  • p is 2 to 10
  • q is 2 or 3
  • R 1 is a methyl group
  • R 2 is an unsubstituted C 1 a straight-chain or branched alkoxy group having ⁇ C 4
  • p is 2 to 8, more preferable q is 3
  • R 1 is a methyl group
  • C 1 ⁇ of R 2 is unsubstituted More preferably, it is a C 3 linear or branched alkoxy group
  • p is 2 to 6 and q is 3.
  • Examples of the C 1 to C 3 alkyl group which may have a substituent of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 include, for example, methyl group, ethyl group, n And -propyl and isopropyl.
  • the alkyl group of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 may be each independently unsubstituted.
  • R 4, R 5, and at least one of R 6 is an alkyl group ⁇ C 3 C 1 may have a substituent group, these two are good C 1 ⁇ optionally having substituent may be an alkyl group of C 3, all three may be an alkyl group ⁇ C 3 C 1 may have a substituent group.
  • At least one of R 7 , R 8 and R 9 is an optionally substituted C 1 to C 3 alkyl group, and two of these may be substituted C 1 to C It may be 3 alkyl groups, or all 3 may be C 1 to C 3 alkyl groups which may have a substituent.
  • Examples of the substituent of the hydrolyzable group of R 2 and the alkyl group of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 include, for example, a halogen atom (a fluorine atom, a chlorine atom, bromine atom, iodine atom), a carboxy group, hydroxy group, amino group, C 1 ⁇ C 6 alkyl mono- or di-substituted amino group, acyl, C 1 ⁇ C 6 alkyl group and the like.
  • the number of substituents is not particularly limited, and the number of substituents of the hydrolyzable group of R 2 is 1 to 5.
  • the number of substituents of the alkyl group of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is one, two or three.
  • silane coupling agent (A) represented by the general formula (1) include (meth) acryloyloxymethyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyl Oxypropyltrimethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyl Trimethoxysilane, 8- (Meth) acryloyloxyoctyltrimethoxysilane, 9- (Meth) acryloyloxynonyltrimethoxysilane, 10- (Meth) acryloyloxydecyltrimethoxysilane, 11- (Meth)
  • alkylene group represented by-(CH 2 ) p- when the alkylene group represented by-(CH 2 ) p- is moderately long, it is well compatible with the polymerizable monomer in the self-adhesive dental composite resin, and as a self-adhesive dental composite resin From the point that the content of the filler (e) contained can be sufficiently increased, and if the alkylene group represented by-(CH 2 ) p- is appropriately short, the hydrophobicity will not be too strong and the adhesion strength will increase.
  • organosilazane (B) represented by General formula (2) the hydroxyl group which exists on the surface of a filler (e), and the hydroxyl group derived from the silane coupling agent (A) represented by General formula (1) Any one may be used as long as it bonds by a deammonia reaction, but it is preferable to use one having a small molecular weight.
  • the treatment amount of the filler (e) with the silane coupling agent (A) represented by the general formula (1) is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the filler (e) before surface treatment 1 to 10 parts by mass is more preferable, and 2 to 8 parts by mass is particularly preferable. If the amount is less than 0.5 parts by mass, a sufficient polymerizable group can not be provided on the surface of the filler (e), and the mechanical strength may be reduced.
  • silane coupling agent (A): organosilazane (B) 1: 1 to 1:20 Is preferable, and 1: 2 to 1:10 is more preferable.
  • organosilazane (B) is smaller than that of the silane coupling agent (A)
  • aggregation may proceed in the paste and the transparency during the storage period may not be ensured, and the silane represented by formula (1)
  • organosilazane (B) represented by the general formula (2) exceeds 20 moles relative to 1 mole of the coupling agent (A)
  • the hydrophobicity may be so strong that sufficient adhesive strength may not be obtained. is there.
  • polymerization inhibitor in order to suppress superposition
  • the polymerization inhibitor known ones such as 3,5-dibutyl-4-hydroxytoluene (BHT) and p-methoxyphenol (methquinone) can be used.
  • the surface treatment agent used for the surface treatment of the filler (e) is substantially only the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2) Those containing are preferred. Substantially containing only the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2) is represented by the general formula (1).
  • the content of the surface treatment agent other than the silane coupling agent (A) and the organosilazane (B) represented by the general formula (2) is less than 1.0% by mass, preferably less than 0.5% by mass. It means that it is less than 0.1% by mass, more preferably.
  • Solidification is a step of precipitating the surface-treated filler (e) with a mineral acid, and washing the precipitate with water and / or dehydrating (eg, drying) to obtain a solid of the filler (e).
  • the conventional filler surface-treated only with the silane coupling agent (A) represented by the general formula (1) is very susceptible to aggregation, so once solidified it is highly dispersed again Have difficulty.
  • the filler (e) of the present invention is difficult to aggregate, it is difficult to aggregate even if it is solidified, and it is easy to redisperse even if it is aggregated.
  • the filler (e) As described above, by washing the filler (e) with water, it is possible to easily produce the filler (e) containing few ionic impurities such as alkali metals. By using the filler (e) containing few ionic impurities, it is possible to maintain the repulsive force between the above-mentioned alkyl groups for a longer time, maintain the high transparency of the paste for a longer time, and to carry out the acidic group-containing (meth) acrylic polymerization.
  • the filler (e) containing few ionic impurities such as alkali metals.
  • washing is preferably repeated until the electric conductivity of the extracted water of the filler (e) (for example, water soaked with the filler (e) for 24 hours at 121 ° C.) becomes 50 ⁇ S / cm or less. .
  • mineral acids used for solidification include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and hydrochloric acid is particularly preferable.
  • a mineral acid may be used as it is, it is preferable to use as a mineral acid aqueous solution. 0.1 mass% or more is preferable, and, as for the density
  • the amount of the mineral acid aqueous solution can be about 6 to 12 times based on the mass of the filler (e) to be cleaned.
  • Washing with the mineral acid aqueous solution can also be performed multiple times. It is preferable to stir after washing
  • the washing with water may be carried out by dispersing and suspending the filler (e) in the same manner as washing with an aqueous solution of mineral acid, followed by filtration, and water is continuously passed through the collected filler (e). May be
  • the end time of washing with water may be judged by the electric conductivity of the above-mentioned extracted water, or it may be a time when the alkali metal concentration in the waste water after washing the filler (e) becomes 1 ppm or less. The point may be when the alkali metal concentration of the extracted water is 5 ppm or less.
  • cleaning with water it can also heat above normal temperature.
  • Drying of the filler (e) can be carried out by a conventional method. For example, it may be left under heating and reduced pressure (vacuum).
  • the heating device and the pressure reducing device are not particularly limited, and known ones can be used.
  • an aqueous organic solvent having a boiling point higher than that of water is added to the water-containing filler (e), and then a mixed material soluble in the aqueous organic solvent is mixed And a method of removing water can be used.
  • propylene glycol monomethyl ether propylene glycol-1-methyl ether, boiling point about 119 ° C .; propylene glycol 2-methyl ether, boiling point about 130 ° C.
  • butanol butanol
  • N-methyl -2-pyrrolidone butylene glycol
  • ⁇ -butyrolactone butyrolactone
  • the content of the filler (e) is a polymerizable monomer because it has sufficient mechanical strength after polymerization and curing by visible light irradiation and is excellent in property stability of the paste during storage over a long period before polymerization and curing. 25 parts by mass or more is preferable, 50 parts by mass or more is more preferable, and 100 parts by mass or more is more preferable from the viewpoint that the self-adhesive dental composite resin has higher mechanical strength with respect to 100 parts by mass of the total amount of components .
  • the content of the filler (e) is preferably 25 to 400 parts by mass, more preferably 50 to 350 parts by mass, and 100 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer. More preferable.
  • the filler (d) and the filler (e) form an electrostatic association state, and the mass ratio of the filler (d) to the filler (e) is excellent because the paste is more excellent in properties such as sag, surface hardness, and dischargeability.
  • the filler (d): filler (e) is preferably 0.05 to 15: 100, more preferably 0.1 to 10: 100, and still more preferably 0.5 to 5: 100.
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) used in the present invention will be described.
  • the (meth) acrylic polymerizable monomer means a (meth) acrylate polymerizable monomer and / or a (meth) acrylamide polymerizable monomer.
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) is an essential component for the self-adhesive dental composite resin of the present invention to exhibit adhesiveness.
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) has an action of decalcifying dentin.
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) has at least one acidic group such as phosphoric acid group, phosphonic acid group, pyrophosphoric acid group, carboxylic acid group and sulfonic acid group, and acryloyl group It is a polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, an acrylamide group and a methacrylamide group.
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) has any one of an acryloyl group, a methacryloyl group, an acrylamide group or a methacrylamide group as a polymerizable group It is preferred to be monofunctional. Specific examples include the following.
  • Examples of the phosphoric acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acryloyloxyethyl hydrogen phosphate, 3- (meth) acryloyl oxypropyl hydrogen phosphate, 4- (meth) acryloyloxy Butyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyl oxyhexyl dihydrophosphate, 7- (meth) acryloyloxyheptyl dihydrophosphate, 8- (meth) acryloyloxyoctyl dihydro Gen phosphate, 9- (meth) acryloyl oxynonyl dihydrophosphate, 10- (meth) acryloyl oxydecyl dihydrophosphate, 11- (meth) a 2- (meth) acryloyloxy dodecyl dihydrophosphate, 16- (meth
  • Examples of the phosphonic acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acryloyloxyethyl phenyl phosphonate, 5- (meth) acryloyl oxypentyl 3-phosphonopropionate, 6- ( Meta) acryloyloxyhexyl 3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl phosphonoacetate, 10- (meth) acryloyloxy And decyl phosphono acetate, acid chlorides, alkali metal salts, ammonium salts, and amine salts of these.
  • pyrophosphate group-containing (meth) acrylic polymerizable monomer for example, bis [2- (meth) acryloyloxyethyl] pyrophosphate, bis [4- (meth) acryloyloxybutyl] pyrophosphate, bis pyrophosphate [6- (Meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, acid chlorides thereof, alkali metal salts, ammonium And salts and amine salts.
  • Examples of the carboxylic acid group-containing (meth) acrylic polymerizable monomer include (meth) acrylic acid, 4- [2-[(meth) acryloyloxy] ethoxycarbonyl] phthalic acid, 4- (meth) acryloyloxy Ethyltrimellitic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloylyl acid Oxydecyloxycarbonyl phthalic acid and acid anhydrides thereof; 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1, 1-octane dicarboxylic acid,
  • sulfonic acid group-containing (meth) acrylic polymerizable monomers examples include 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, acid chlorides thereof, alkali metal salts And ammonium salts and amine salts.
  • a carboxylic acid group-containing (meth) acrylic polymerizable monomer is preferable because it exhibits better adhesion to the tooth substance, and in particular, a phosphoric acid group-containing (meth) acrylic polymerizable monomer, And carboxylic acid group-containing (meth) acrylic polymerizable monomers are preferable.
  • a phosphoric acid group-containing (meth) acrylate monofunctional polymerizable monomer or a carboxylic acid having an alkylene group of alkyl or C 6 ⁇ C 20 of C 6 ⁇ C 20 as a main chain in the molecule The (meth) acrylate-based polymerizable monomer is more preferable, and the phosphoric acid group-containing (meth) acrylate-based monofunctional polymerizable monomer having a C 8 to C 12 alkylene group as a main chain in the molecule is further preferable preferable.
  • 10-methacryloyloxydecyl hydrogenogen phosphate 4- (meth) acryloyloxyethyl trimellitic acid and 4- (meth) acryloyloxyethyl trimellitic anhydride are preferred, and 10-methacryloyloxydecyl dihydrophosphate is most preferred .
  • the acidic group-containing (meth) acrylic polymerizable monomer (a) may be used singly or in combination of two or more.
  • the content of the acidic group-containing (meth) acrylic polymerizable monomer (a) is not particularly limited as long as the effects of the present invention are exhibited, but the total content of the polymerizable monomer component is higher in terms of higher adhesive strength.
  • the range of 1 to 40 parts by mass is preferable, the range of 2 to 20 parts by mass is more preferable, the range of 3 to 20 parts by mass is more preferable, and the range of 4 to 20 parts by mass is most preferable.
  • the content of a certain polymerizable monomer in 100 parts by mass of the total amount of the polymerizable monomer component refers to the case where the total amount of the polymerizable monomer component is 100% by mass. It means the content (% by mass) of the polymerizable monomer. Therefore, the total amount of the respective polymerizable monomer components does not exceed 100 parts by mass.
  • the polyfunctional (meth) acrylic-type polymerizable monomer (b) which does not contain the acidic group used by this invention is demonstrated.
  • the polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group has no acidic group in the molecule and at least two polymerizable groups.
  • the polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group has the effect of improving the handleability or mechanical strength of the self-adhesive dental composite resin of the present invention, Group-based difunctional polymerizable monomers, aliphatic compound-based difunctional polymerizable monomers, trifunctional or higher polymerizable monomers, and the like.
  • aromatic compound-based difunctional polymerizable monomer examples include, for example, 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth) acryloyloxy- 2-Hydroxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane (average of ethoxy groups) With an addition number of moles of 2.6), 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2 , 2-Bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acrylic acid Iyloxypentaethoxyphenyl) propane, 2,2-bis (4- (
  • Examples of aliphatic compound difunctional polymerizable monomers include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene.
  • Glycol di (meth) acrylate butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) di (meth) acrylate, 1,2-bis (3-Metak Roiruokishi-2-hydroxypropoxy) bifunctional such as ethane (meth) acrylate compounds, and the like.
  • trifunctional or higher polymerizable monomers include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra
  • trifunctional or higher (meth) acrylate compounds such as (meth) acrylate and 1,7-diacryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxaheptane.
  • N, N '-(2,2,4-trimethylhexamethylene) bis [2- (amin
  • bifunctional polymerizable monomers of aromatic compound type in view of mechanical strength or handleability
  • a difunctional polymerizable monomer of a group compound type is used.
  • a bifunctional polymerizable monomer based on an aromatic compound 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (generally called “Bis-GMA”), and 2, 2-Bis (4-methacryloyloxypolyethoxyphenyl) propane (having an average addition mole number of ethoxy groups of 2.6, commonly called “D-2.6E”) is preferred.
  • aliphatic compound difunctional polymerizable monomers examples include glycerol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (generally called “TEGDMA”), neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, and 2,2,4-trimethyl Hexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (commonly called "UDMA”) is preferred.
  • TEGDMA triethylene glycol diacrylate
  • TEGDMA triethylene glycol dimethacrylate
  • neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate
  • the polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group may be used alone or in combination of two or more.
  • the content of the polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group is not particularly limited as long as the effects of the present invention are exhibited, but the dental composition (self-adhesive dental composite resin) 30 to 95 parts by mass in 100 parts by mass of the polymerizable monomer component in the self-adhesive dental composite resin from the viewpoint of having high permeability to the tooth material and excellent adhesion and having sufficient strength
  • the range of 40 to 90 parts by mass is more preferable, the range of 50 to 85 parts by mass is more preferable, and the range of 60 to 80 parts by mass is most preferable.
  • the self-adhesive dental composite resin of the present invention may further contain a multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton as a polymerizable monomer component.
  • the multifunctional (meth) acrylamide polymerizable monomer (f) having at least one or more amide protons has high hydrophilicity since it has at least one or more amide protons, and penetrates into the collagen layer of dentin And because it has multiple polymerizable groups in the molecule, together with the other components of the self-adhesive dental composite resin, it exhibits a very high degree of hardenability, resulting in higher adhesion to dentin. can get.
  • a polyfunctional (meth) acrylamide polymerizable monomer (f) As a polyfunctional (meth) acrylamide polymerizable monomer (f), a table with a multifunctional (meth) acrylamide polymerizable monomer (f1) represented by the following general formula (3), and the following general formula (4) Examples thereof include polyfunctional (meth) acrylamide polymerizable monomers (f2) and polyfunctional (meth) acrylamide polymerizable monomers (f3) represented by the following general formula (5).
  • R 10 , R 11 and R 12 are each independently a hydrogen atom or a methyl group, s is an integer of 1 to 6, and X 1 and X 2 are each independently a substitution A C 1 to C 8 linear or branched alkylene group which may have a group)
  • R 13 and R 14 each independently represent a hydrogen atom or a methyl group, t is 2 or 3, and X 3 and X 4 each independently have a substituent) (C 1 to C 8 linear or branched alkylene group)
  • Z is a C 1 to C 8 linear or branched aliphatic group or aromatic group which may have a substituent, and the aliphatic group is —O—, —S, -, - CO -, - CO -O -, - O-CO -, - NR 15 -, - CONR 15 -, - NR 15 -CO -, - CO-O-NR 15 -, - O-CONR R 15 may be interrupted by at least one bonding group selected from the group consisting of 15 — and —NR 15 —CO—NR 15 — R 15 may be a hydrogen atom or a C 1 optionally having a substituent. It represents a linear or branched chain aliphatic group of ⁇ C 8.
  • R 10 , R 11 , R 12 , R 13 and R 14 are preferably hydrogen atoms from the viewpoint of adhesion to dentin and polymerization curing.
  • s is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. It is preferable that t is three.
  • Examples of the C 1 to C 8 linear or branched alkylene group which may have a substituent of X 1 , X 2 , X 3 and X 4 include, for example, a methylene group, a methyl methylene group and an ethylene group 1-methylethylene group, 2-methylethylene group, trimethylene group, 1-ethylethylene group, 2-ethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group , 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, 1-propylethylene group, 2-propylethylene group, 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group 1,1,2-trimethylethylene, 1,2,2-trimethylethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 3-ethyltrime Tylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxy group, a hydroxy group, an amino group, C 1 to C 8 Alkyl group mono- or di-substituted amino group, acyl group, acyloxy group, amide group, C 2 -C 8 alkoxycarbonyl group, C 1 -C 8 alkoxy group, C 1 -C 8 alkylthio group, C 1 -C 8 alkyl groups and the like are preferable, and halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), C 1 to C 8 alkyl groups and the like are more preferable.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group and isopentyl Groups, n-hexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group and the like.
  • the alkyl group is preferably a linear or branched C 1 to C 4 alkyl group.
  • the number of substituents is not particularly limited, and may be about 1 to 8, preferably one, two or three.
  • the C 1 to C 8 aliphatic group which may have a substituent represented by Z is a saturated aliphatic group (alkylene group, cycloalkylene group (eg, 1,4-cyclohexylene group etc.))
  • unsaturated aliphatic group an alkenylene group, an alkynylene group
  • a saturated aliphatic group alkylene group
  • Z is preferably a linear or branched C 1 to C 4 aliphatic group which may have a substituent, from the viewpoint of adhesiveness to dentin and polymerization curing property, and Z has a substituent It is more preferable that it is a linear or branched C 2 -C 4 aliphatic group which may be substituted.
  • Examples of the C 1 to C 8 alkylene group include the same as X 1 , X 2 , X 3 and X 4 .
  • an aromatic group which may have a substituent represented by Z an aryl group and an aromatic heterocyclic group are mentioned, for example.
  • an aryl group is preferable to an aromatic heterocyclic group.
  • the heterocycle of the aromatic heterocycle group is generally unsaturated.
  • the aromatic heterocycle is preferably a 5- or 6-membered ring.
  • a phenyl group is preferable, for example.
  • aromatic heterocyclic group for example, furan group, thiophene group, pyrrole group, oxazole group, isoxazole group, thiazole group, isothiazole group, imidazole group, pyrazole group, frazane group, triazole group, pyran group, pyridine Groups, pyridazine groups, pyrimidine groups, pyrazine groups, and 1,3,5-triazine groups.
  • a phenyl group is particularly preferred.
  • the aliphatic group in R 15 may be any of a saturated aliphatic group (alkyl group) and an unsaturated aliphatic group (alkenyl group, alkynyl group), and is easy to obtain or manufacture and has chemical stability. From the point of view, saturated aliphatic groups (alkyl groups) are preferred. Examples of the alkyl group include C 1 to C 8 alkyl groups similar to those described as the substituents for X 1 , X 2 , X 3 , and X 4 .
  • R 15 is more preferably a hydrogen atom or a linear or branched C 1 to C 4 alkyl group which may have a substituent, and a hydrogen atom or a linear or branched group which may have a substituent More preferred are C 1 -C 3 alkyl groups in the chain.
  • the aliphatic groups of Z may be interrupted by at least one linking group as described above. That is, at least one bonding group may be inserted into the aliphatic group.
  • the number of linking groups is not particularly limited, but may be about 1 to 10, preferably one, two or three. And more preferably one or two.
  • the aliphatic group of Z is not interrupted by the continuous bonding group. That is, it is preferable that the bonding groups are not adjacent to each other.
  • the compound (f1-1), the compound (f1-3), the compound (f1-5) and the compound (f1-7) are preferable from the viewpoints of the adhesiveness to the tooth substance and the polymerization curing property, and the compound (f1-) 1)
  • the compound (f1-5) is more preferable, and the compound (f1-5) is most preferable from the viewpoint of hydrophilicity involved in penetration of dentin into the collagen layer.
  • the compound (f2-1), the compound (f2-3), the compound (f2-5) and the compound (f2-7) are preferable from the viewpoint of adhesion to dentin and polymerization curing property, and the compound (f2-2) is preferable.
  • the compound (f2-3) is more preferable, and the compound (f2-1) is most preferable from the viewpoint of the hydrophilicity involved in the penetration of dentin into the collagen layer.
  • Multifunctional (Meth) Acrylamide Polymerizable Monomer (f3) Represented by the Above Formula (5) (Hereinafter, Also Referred to as Asymmetric Multifunctional (Meth) Acrylamide Polymerizable Monomer (f3)) Although it does not specifically limit as this, The thing shown below is mentioned.
  • Ethyl) acrylamide, N- (2- (2-methacryloyloxyethoxy) ethyl) acrylamide is more preferable
  • methacryloyloxypropyl acrylamide is methacryloyloxypropyl acrylamide.
  • the polyfunctional (meth) acrylamide polymerizable monomer (f) having at least one or more amide protons one type may be used alone, or two or more types may be used in combination.
  • a group comprising a polyfunctional (meth) acrylamide polymerizable monomer (f3), a polyfunctional (meth) acrylamide polymerizable monomer (f1) and a polyfunctional (meth) acrylamide polymerizable monomer (f2) It may be a combination with one or more polymerizable monomers selected from
  • the content of the polyfunctional (meth) acrylamide polymerizable monomer (f) is not particularly limited as long as the effects of the present invention are exhibited, but the content is 0.5 to 5 parts by mass in 100 parts by mass of the polymerizable monomer component.
  • the range of 30 parts by mass is preferable, the range of 2 to 25 parts by mass is more preferable, the range of 2.5 to 28 parts by mass is more preferable, and the range of 3 to 20 parts by mass is most
  • the self-adhesive dental composite resin of the present invention may or may not further contain a hydrophilic monofunctional polymerizable monomer (g) as a polymerizable monomer component.
  • the hydrophilic monofunctional polymerizable monomer (g) has a solubility in water at 25 ° C. of 5% by mass or more and is monofunctional polymerizable other than the above (a), the above (b) and the above (f) It means a monomer, the one having the same solubility of 10% by mass or more is preferable, and the one having the same solubility of 15% by mass or more is more preferable.
  • the hydrophilic monofunctional polymerizable monomer (g) has at least one or more hydrophilic groups such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, and an amide group.
  • hydrophilic monofunctional polymerizable monomer (g) 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl
  • Hydrophilic monofunctional (meth) acrylate type polymerizable monomer such as (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-trimethylammonium ethyl (meth) acrylic chloride; N-methylol (meth) ) Acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, N-methoxymethyl (meth)
  • R 16 and R 17 are each independently a linear or branched C 1 to C 3 alkyl group which may have a substituent, and R 18 is a hydrogen atom or a methyl group. is there.
  • Examples of the substituent in R 16 and R 17 include the same as the substituents in X 1 , X 2 , X 3 and X 4 .
  • Examples of the C 1 to C 3 alkyl group for R 16 and R 17 include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
  • hydrophilic monofunctional polymerizable monomers (g) 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate and diacetone (meth )
  • Monofunctional (meth) acrylamide-based polymerizable monomers represented by acrylamide and general formula (6) are preferable, and monofunctional (meth) acrylamide-based polymerizable monomers represented by general formula (6) Is more preferred.
  • the hydrophilic monofunctional polymerizable monomer (g) may be used alone or in combination of two or more.
  • N, N-dimethyl acrylamide and N, N-diethyl acrylamide are more preferable from the viewpoint of storage stability.
  • N, N-diethylacrylamide is most preferred.
  • the content of the hydrophilic monofunctional polymerizable monomer (g) in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of showing a sufficient adhesive strength improvement effect and mechanical strength, self
  • the total amount of 100 parts by mass of the polymerizable monomer component in the adhesive dental composite resin is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 2 to 28 parts by mass, and in the range of 5 to 25 parts by mass More preferably, the range of 7 to 20 parts by mass is particularly preferable.
  • the self-adhesive dental composite resin of the present invention has an acidic group-containing (meth) acrylic polymer within a range that does not impair the effects of the present invention for the purpose of improving adhesion, handleability, mechanical strength, etc.
  • a polymerizable monomer (j) other than the monofunctional polymerizable monomer (g) may be blended.
  • Examples of the polymerizable monomer (j) include hydrophilic polyfunctional (meth) acrylate type polymerizable monomers (j1) and / or symmetrical (meth) acrylamide compounds (j2).
  • the hydrophilic polyfunctional (meth) acrylate-based polymerizable monomer (j1) has a solubility in water at 25 ° C. of 5% by mass or more and is not limited to (a), (b), and (f). It means a functional polymerizable monomer, preferably having a solubility of 10% by mass or more, and more preferably one having a solubility of 15% by mass or more.
  • hydrophilic polyfunctional (meth) acrylate type polymerizable monomer (j1) for example, pentaerythritol di (meth) acrylate, erythritol di (meth) acrylate, mannitol di (meth) acrylate, xylitol di (meth) Acrylate, sorbitol di (meth) acrylate and the like.
  • examples of the symmetrical (meth) acrylamide compound (j2) include N, N'-ethylenebisacrylamide, N, N'-diethyl-1,3-propylenebisacrylamide and the like.
  • the polymerizable monomer (j) one type may be used alone, or two or more types may be used in combination.
  • the total content of polymerizable monomers contained in the self-adhesive dental composite resin of the present invention is preferably less than 49.9% by mass with respect to the entire self-adhesive dental composite resin, and 44.5 mass. Less than% is more preferable, and less than 40.0% by mass is more preferable. Moreover, 9.0 mass% or more is preferable with respect to the whole self-adhesive dental composite resin, as for content of the sum total of a polymerizable monomer, 14.0 mass% or more is more preferable, and 19.0 mass%. The above is more preferable.
  • the photopolymerization initiator (c) in the present invention is a component that accelerates the polymerization and curing of the self-adhesive dental composite resin.
  • the photopolymerization initiator (c) can be selected from known photopolymerization initiators, and among them, the photopolymerization initiator used for dental use is preferably used.
  • the photopolymerization initiator (c) may be used alone or in combination of two or more.
  • photopolymerization initiator (c) for example, (bis) acyl phosphine oxides, water-soluble acyl phosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, ⁇ -diketones, coumarins, Anthraquinones, benzoin alkyl ether compounds, ⁇ -amino ketone compounds and the like can be mentioned.
  • a self-adhesive dental composite resin is excellent in photo-curing properties in the visible and near-ultraviolet regions and exhibits sufficient photo-curing properties using any light source of halogen lamp, light emitting diode (LED) and xenon lamp. can get.
  • acyl phosphine oxides examples include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide, 2,6-dichloro benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl Examples thereof include methoxyphenyl phosphine oxide, 2,4,6-trimethyl benzoyl ethoxy phenyl phosphine oxide, 2,3,5,6- tetramethyl benzoyl diphenyl phosphine oxide, benzoyl di- (2,6-dimethylphenyl) phosphonate and the like. Among these, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is preferable.
  • bisacyl phosphine oxides include bis (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, and bis (2,6-dichloro).
  • Benzoyl) -4-propylphenyl phosphine oxide bis (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4,4-trimethylpentyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis (2,5,5 6-trime Rubenzoiru) -2,4,4-trimethyl pentyl phosphine oxide and the like.
  • bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide is preferable.
  • ⁇ -diketones examples include diacetyl, benzyl, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone and the like. Can be mentioned. Among these, dl-camphor quinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light range.
  • Examples of the coumarin compounds include 3,3′-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3 -Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p- Nitrobenzoyl) coumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [F] coumarin, 3-carboxy coumarin, 3-carboxy 7-Methoxycoumarin, 3-Ethoxycarbonyl-6-methoxycoumarin,
  • the content of the photopolymerization initiator (c) is not particularly limited, but from the viewpoint of the curability and the like of the resulting self-adhesive dental composite resin, it is 0 with respect to 100 parts by mass in total of the polymerizable monomer component. .001 to 20 parts by mass is preferable, 0.05 to 10 parts by mass is more preferable, and 0.10 to 5 parts by mass is more preferable.
  • content of a photoinitiator (c) is less than 0.001 mass part with respect to 100 mass parts of total amounts of a polymerizable monomer component, superposition
  • polymerization does not fully advance but causes the fall of adhesive strength.
  • the self-adhesive dental composite resin of the present invention may further contain a chemical polymerization initiator.
  • An organic peroxide is preferably used as a chemical polymerization initiator.
  • the organic peroxide is not particularly limited, and known ones can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxy esters, peroxy dicarbonates, and the like. As specific examples of these organic peroxides, those described in WO 2008/087977 can be mentioned.
  • the chemical polymerization initiators may be used alone or in combination of two or more.
  • the filler (i) which is not the filler (d) and is not the filler (e) affects the appropriate dischargeability, fluidity, sag and surface hardness. You may include in the range which is not.
  • the filler (i) is a filler that has an isoelectric point of less than 6.0, and is not treated with a surface treatment agent that contains both the silane coupling agent (A) and the organosilazane (B),
  • the component is intended to impart radiopacity to a self-adhesive dental composite resin, or to improve the strength or paste operability as a matrix.
  • radiopaque refers to the ability of the solidified dental material to be distinguished from tooth structures using standard dental x-ray equipment in a conventional manner. Radiopacity in dental materials is advantageous in certain cases where x-rays are used to diagnose the condition of the teeth.
  • filler (i) known fillers used in dental composite resins are used without any limitation, as long as they do not correspond to the filler (d) and the filler (e).
  • the filler for example, liquid phase synthetic amorphous silica, fumed silica, fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (pyrex glass), etc.
  • Powders of various compositions dental glass powders such as barium glass, strontium borosilicate glass, lanthanum glass ceramics, fluoroaluminosilicate glass, etc., composite oxides such as silica-titania and silica-zirconia, and surfaces coated with silica Core-shell structure calcium fluoride, silica surface-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium-fluoride, silica surface-coated core-shell structure calcium phosphate, silica surface The Core-shell structure barium sulfate, silica surface-coated core-shell structure zirconium dioxide, silica surface-coated core-shell structure titanium dioxide, silica surface-coated core-shell structure hydroxyapatite Be One of these may be used alone, or two or more may be used in combination.
  • dental glass powders such as barium glass, strontium borosilicate glass, lanthanum
  • those having a silica surface are preferable in that they can be treated with the silane coupling agent (A) and form an electrostatically weak association state with the filler (d) having an isoelectric point of 6.0 or more.
  • fumed silica, ytterbium fluoride having a core-shell structure surface-coated with silica, and yttrium fluoride having a core-shell structure coated with silica are preferable.
  • the average particle diameter of the filler (i) is preferably 0.001 to 50.0 ⁇ m, more preferably 0.005 to 20.0 ⁇ m, and still more preferably 0.008 to 10.0 ⁇ m, and 0.01 to 4.50 ⁇ m. Is particularly preferred. Within these ranges, sufficient mechanical strength can be obtained, no stickiness occurs in the paste, no problem occurs in operability, and the abrasion resistance and lubricity durability of the cured product are excellent.
  • the average particle size of the filler (i) can be measured in the same manner as the method of measuring the average particle size of the filler (d) or the filler (e) described above.
  • the filler (i) is preferably treated with a surface treatment agent.
  • surface treatment agents include at least one organometallic compound selected from the group consisting of organosilicon compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds, and the silane coupling agent (A) and The surface treatment agent which contains the said organosilazane (B) together is remove
  • it may be a surface treatment layer of a mixture of two or more kinds of organic metal compounds, or as a surface treatment layer of a multilayer structure in which two or more kinds of organic metal compound layers are laminated. Good.
  • organosilicon compounds include the compounds represented by (W) n SiY 4-n mentioned as the surface treatment agent for the filler (d) (in the formula, the symbols have the same meanings as described above).
  • a coupling agent having a functional group copolymerizable with the polymerizable monomer component such as ⁇ - (meth) acryloyloxyalkyltrimethoxysilane (a carbon between a (meth) acryloyloxy group and a silicon atom Number: 3 to 12), ⁇ - (meth) acryloyloxyalkyltriethoxysilane (number of carbons between (meth) acryloyloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and the like are particularly preferably used.
  • ⁇ - (meth) acryloyloxyalkyltrimethoxysilane a carbon between a (meth) acryloyloxy group and a silicon atom Number: 3 to 12
  • organic titanium compound examples include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and the like.
  • organic zirconium compound examples include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconyl acetate and the like.
  • organoaluminum compound examples include aluminum acetylacetonate, and an aluminum organic acid salt chelate compound.
  • the shape of the filler (i) is not particularly limited and may be appropriately selected according to the properties desired to be enhanced as a dental composite resin, and specifically, it can be used as a powder of amorphous or spherical particles .
  • the use of the indeterminate filler (i) is particularly excellent in mechanical strength and abrasion resistance, and the use of the spherical filler (i) is particularly excellent in polishing lubricity and lubricity durability.
  • the filler (i) in the present invention may be a commercially available product.
  • the content of the filler (i) is not particularly limited as long as the effects of the present invention are exhibited, but a range of 1 to 100 parts by mass is preferable and a range of 3 to 90 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Is more preferable, and the range of 5 to 80 parts by mass is particularly preferable. Within these ranges, sufficient radiopacity of the cured product or sufficient mechanical strength can be obtained, and sufficient paste operability can be obtained.
  • the above-mentioned fumed silica can be suitably used as a filler (i) for the purpose of providing leveling to a paste.
  • the above-mentioned fumed silica is a silica which is produced dry by combustion hydrolysis using silicon tetrachloride as a precursor, and may or may not be blended in the self-adhesive dental composite resin of the present invention. And may be blended for the purpose of adjusting the leveling properties of the paste.
  • the leveling property of a paste is a characteristic in which the corner of the paste taken out of the container disappears by its own weight.
  • the BET specific surface area (specific surface area according to BET (Brunauer-Emmett-Teller) method) of the fumed silica is preferably 25 m 2 / g or more, more preferably 50 m 2 / g or more, from the viewpoint of imparting the leveling property of the paste. 100 m 2 / g or more is more preferable. Moreover, in the viewpoint which does not impair the leveling property of a self-adhesive dental composite resin, 400 m ⁇ 2 > / g or less is preferable, 350 m ⁇ 2 > / g or less is more preferable, 250 m ⁇ 2 > / g or less is more preferable. Therefore, from the point of view, BET specific surface area of the fumed silica is preferably 25 ⁇ 400m 2 / g, more preferably 50 ⁇ 350m 2 / g, more preferably 100 ⁇ 250m 2 / g.
  • the average primary particle diameter of the fumed silica is preferably 5 nm or more, more preferably 7 nm or more, and still more preferably 10 nm or more from the viewpoint of not deteriorating the leveling property of the paste. Moreover, in the viewpoint which provides the leveling property of a paste, 50 nm or less is preferable, 30 nm or less is more preferable, and 20 nm or less is more preferable. Therefore, from the above viewpoint, the average primary particle diameter of fumed silica is preferably 5 to 50 nm, more preferably 7 to 30 nm, and still more preferably 10 to 30 nm.
  • the pH of the fumed silica is preferably 3.0 or more, more preferably 3.5 or more, and 4.0 or more, from the viewpoint of not affecting the other components in the self-adhesive dental composite resin of the present invention. Is more preferred. Further, in view of suppressing the reaction with the acidic group-containing (meth) acrylic polymerizable monomer (a), 10.0 or less is preferable, 9.0 or less is more preferable, and 8.0 or less is more preferable. Therefore, from the above viewpoint, the pH of fumed silica is preferably 3.0 to 10.0, more preferably 3.5 to 9.0, and still more preferably 4.0 to 8.0.
  • the apparent specific gravity of the fumed silica is preferably 20 g / L or more, more preferably 50 g / L or more, and still more preferably 120 g / L or more, from the viewpoint of suppressing an increase in viscosity when compounded. Further, from the viewpoint of a higher effect of imparting fluidity to the paste by the bearing effect, the amount is preferably 300 g / L or less, more preferably 290 g / L or less, and still more preferably 280 g / L or less. Therefore, from the above viewpoint, the apparent specific gravity of the fumed silica (d) is preferably 20 to 300 g / L, more preferably 50 to 290 g / L, and still more preferably 120 to 280 g / L.
  • the fumed silica preferably has a BET specific surface area of 50 to 350 m 2 / g and an apparent specific gravity of 50 to 290 g / L, BET It is more preferable that the specific surface area is 100 to 250 m 2 / g and the apparent specific gravity is 120 to 280 g / L, and the BET specific surface area is 100 to 250 m 2 / g, and the pH is 4.0 to 8.0.
  • the measuring method of the said chemical property of fumed silica is as follows.
  • Average Primary Particle Size (nm): Taking a picture of a sample with a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) and measuring the particle diameter of particles (200 or more) observed in the unit field of the picture, image analysis type particle size distribution measurement It is determined by measurement using software (Macview (Mountech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter thereof. pH: 4 parts by mass of a sample is dispersed at normal temperature with respect to 100 parts by mass of distilled water to obtain a 4% by mass aqueous dispersion.
  • the pH in the 4% by mass aqueous dispersion is measured with a bench-top pH meter (F71, manufactured by Horiba, Ltd.).
  • the above method conforms to ISO 787-9: 1981 except that a 4% by mass aqueous dispersion is used.
  • Apparent specific gravity The measurement is performed according to the method according to ISO 787-11: 1981, and is calculated by the following equation as Tapped density (also referred to as Tamped density).
  • the fumed silica be treated with the surface treatment agent described above for the filler (i), then be heat-treated and then structurally modified.
  • structurally modifying means raising the apparent specific gravity without significantly changing the BET specific surface area, the average primary particle size, and the pH.
  • the means for structural modification is not particularly limited as long as the apparent specific gravity can be increased without significantly changing the BET specific surface area, the average primary particle size, and the pH. It can be structurally modified by first spraying with water, then spraying with a surface treatment agent, optionally mixing further and then heat treating.
  • the water used may be acidified (pH 1 to 7) with an acid (for example hydrochloric acid), and in the case of using several surface treatments, these surface treatments may be used simultaneously. It may also be used separately once or as a mixture.
  • One or more surface treatment agents may be dissolved in a suitable solvent such as water, ethanol, isopropyl alcohol. Mixing may be continued for an additional 5 to 30 minutes after spraying is complete.
  • the mixture is heat treated at a temperature of 20 to 400 ° C. for 0.1 to 6 hours, and the heat treatment can be performed under a protective gas, for example, under a nitrogen atmosphere.
  • the structurally modified fumed silica has a high apparent specific gravity, so when structurally modified fumed silica and the polymerizable monomer are respectively incorporated in the same amount, the structural modification is made.
  • the dental composition containing self-adhesive fumed silica self-adhesive dental composite resin
  • the apparent specific gravity of the structurally modified fumed silica is preferably 100 to 300 g / L, more preferably 110 to 290 g / L, and still more preferably 120 to 280 g / L from the viewpoint described above.
  • the fumed silica commercially available products can be used.
  • AEROSIL registered trademark
  • R7200 surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m 2 / g, average primary
  • Particle size 12 nm, pH: 4.5, apparent specific gravity: 230 g / L, manufactured by EVONIK INDUSTRIES
  • AEROSIL registered trademark
  • R8200 surface treatment agent: 1,1,1,3,3,3-hexamethyl
  • Disilazane BET specific surface area: 155 m 2 / g, average primary particle diameter: 12 nm, pH: 5.5, apparent specific gravity: 140 g / L, manufactured by EVONIK INDUSTRIES
  • AEROSIL registered trademark
  • R 9200 surface treatment agent
  • BET specific surface area 170 m 2 / g, average primary particle size: 12 n
  • the content of the total of the fillers (filler (d), filler (e) and filler (i)) contained in the self-adhesive dental composite resin of the present invention is 50 with respect to the entire self-adhesive dental composite resin. .0 mass% or more is preferable, 55.0 mass% or more is more preferable, 59.0 mass% or more is more preferable. Moreover, 90.0 mass% or less is preferable with respect to the whole self-adhesive dental composite resin, as for content of the sum total of a filler, 85.0 mass% or less is more preferable, and 80.0 mass% or less is more preferable. .
  • the filler contained in the self-adhesive dental composite resin of the present invention is substantially only the filler (d) and the filler (e)
  • the preferable content is the total of the filler (d) and the filler (e) It is good also as content.
  • a polymerization accelerator (h) is used together with a photopolymerization initiator (c) and / or a chemical polymerization initiator.
  • the polymerization accelerator (h) include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfurous acid Salts, bisulfites, thiourea compounds and the like can be mentioned.
  • the amines are divided into aliphatic amines and aromatic amines.
  • the aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono Tertiary such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Aliphatic amines, and the like.
  • aromatic amine examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis ( 2-Hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N -Bis (2-hydroxyethyl) -4-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3 , 5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N,
  • N, N-bis (2-hydroxyethyl) -p-toluidine and 4- (N, N-dimethylamino) benzoic acid from the viewpoint of being able to impart excellent curability to a self-adhesive dental composite resin.
  • At least one selected from the group consisting of ethyl, n-butoxyethyl 4- (N, N-dimethylamino) benzoate and 4- (N, N-dimethylamino) benzophenone is preferably used.
  • the said polymerization accelerator (h) may be mix
  • the content of the polymerization accelerator (h) is not particularly limited, but from the viewpoint of the curability and the like of the obtained self-adhesive dental composite resin, 0. 0 to 100 parts by mass of the total of the polymerizable monomer components.
  • the amount is preferably 001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.1 to 5 parts by mass.
  • the content of the polymerization accelerator (h) may be 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monomer components.
  • the polymerization accelerator (h) When the content of the polymerization accelerator (h) is less than 0.001 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component, the polymerization may not proceed sufficiently, which may cause a decrease in adhesiveness. is there. On the other hand, when the content of the polymerization accelerator (h) exceeds 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component, sufficient adhesiveness is obtained depending on the polymerization performance of the polymerization initiator itself. In addition, the polymerization accelerator (h) may be precipitated from the self-adhesive dental composite resin.
  • the self-adhesive dental composite resin of the present invention may further contain a fluoride ion-releasing substance (k).
  • a fluoride ion-releasing substance By blending the fluorine ion releasing substance (k), a self-adhesive dental composite resin capable of imparting acid resistance to dentin can be obtained.
  • the fluorine ion-releasing substance include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride and ytterbium fluoride.
  • the fluorine ion-releasing substance (k) may be used alone or in combination of two or more.
  • Preferred embodiments of the self-adhesive dental composite resin of the present invention include a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer contains an acidic group ( Meta) acrylic polymerizable monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and polyfunctional (meth) acrylamide polymerizable monomer having an amide proton
  • the above-mentioned polymerizable monomer contains an acidic group-containing (meth) acrylic polymerizable monomer (a), a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and Hydrophilic monofunctional polymeriz
  • it contains a polymerizable monomer, a photoinitiator (c), and a filler, and the said polymerizable monomer is acidic group containing (meth) acrylic-type polymerizable property.
  • a self-adhesive dental composite resin which contains a basic monofunctional polymerizable monomer (g), and the filler includes a filler (d) and a filler (e).
  • a polymerizable monomer, a photopolymerization initiator (c), and a filler are contained, and the polymerizable monomer is an acidic group-containing (meth) acrylic polymerizable monomer.
  • A a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and a polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton, and hydrophilicity
  • the monofunctional polymerizable monomer (g) and the above-mentioned polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group is an aliphatic compound-based bifunctional polymerizable monomer
  • the polymerizable monomer, the photopolymerization initiator (c), and the filler are contained, and the polymerizable monomer is an acidic group-containing (meth) acrylic polymer.
  • each component can be appropriately changed based on the above description, the type of the compound can be appropriately selected, and any component (for example, polymerization accelerator (h), chemistry A polymerization initiator, a polymerization inhibitor and the like may be added or removed.
  • any component for example, polymerization accelerator (h), chemistry A polymerization initiator, a polymerization inhibitor and the like may be added or removed.
  • the self-adhesive dental composite resin of the present invention may contain a pH adjuster, a polymerization inhibitor, an ultraviolet light absorber, a thickener, a coloring agent, an antibacterial agent, a flavoring agent, etc. within the range not impairing the effects of the present invention. You may mix
  • the self-adhesive dental composite resin of the present invention may be either a one-material type or a divided-type material as a preferable material type. Among them, the single-material type is more preferable from the viewpoint of the simplicity of the operation.
  • the surface hardness (Vickers hardness) of the cured product is preferably 25 to 55 Hv, more preferably 30 to 50 Hv, and preferably 35 to 45 Hv. More preferable.
  • the present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention can be obtained.
  • UDMA 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate
  • Bis-GMA 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane
  • D-2 .6E 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (having an average addition mole number of ethoxy groups of 2.6)
  • TEGDMA triethylene glycol dimethacrylate
  • ALU-C Commercial product (trade name: AEROXIDE (registered trademark) Alu C, BET specific surface area: 100 m 2 / g, average primary particle diameter: 13 nm, pH: 5.0, apparent specific gravity: 50 g / L, EVONIK INDUSTRIES Company company) was used as it was. The isoelectric point was 9.0.
  • ST-ALU-C Commercially available product (trade name: AEROXIDE (registered trademark) Alu C, BET specific surface area: 100 m 2 / g, average primary particle size: 13 nm, pH: 5.0, apparent specific gravity: 50 g / L, An EVONIK INDUSTRIES Inc. product was surface-treated with 10-methacryloyloxydecyl dihydrophosphate and 11-methacryloyloxyundecyl trimethoxysilane. The isoelectric point was 9.0.
  • TAC 4 N, N ', N'',N'''-tetraacryloyltriethylenetetramine (compound represented by the following formula (f1-5))
  • MAEA N-methacryloyloxyethyl acrylamide (asymmetric multifunctional (meth) acrylamide polymerizable monomer represented by the following formula)
  • R 7200 Commercially available product (trade name: AEROSIL (registered trademark) R 7200, surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m 2 / g, average primary particle size: 12 nm, pH: 4.5, apparent) Specific gravity: 230 g / L (manufactured by EVONIK INDUSTRIES) was used as it was.
  • AEROSIL registered trademark
  • surface treatment agent methacryloyloxysilyl group-containing silane compound
  • BET specific surface area 145 m 2 / g
  • average primary particle size 12 nm
  • pH pH: 4.5
  • apparent Specific gravity: 230 g / L (manufactured by EVONIK INDUSTRIES) was used as it was.
  • R 711 Commercially available product (trade name: AEROSIL (registered trademark) R 711, surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 150 m 2 / g, average primary particle size: 12 nm, pH: 4.5, apparent) Specific gravity: 50 g / L (manufactured by EVONIK INDUSTRIES) was used as it was.
  • SiO 2 coated YBF silica-coated ytterbium fluoride: A commercially available product (SG-YBF100 WSCMP10, average particle diameter 110 nm, spherical particles, manufactured by Sukkyung AT) was used as it was.
  • HMDS 1,1,1,3,3,3-hexamethyldisilazane
  • a dispersion of silica particles dispersed in a liquid medium is obtained by adding 60 parts by mass of isopropanol to 100 parts by mass of a slurry in which silica particles are dispersed in water at a concentration of 20% by mass and mixing at room temperature (about 25.degree. C.). Obtained.
  • silica particles were surface-treated to obtain a silica particle material.
  • hydrophobicized silica particles can not be stably present in water and isopropanol, and aggregate and precipitate.
  • the molar ratio of 3-methacryloyloxypropyltrimethoxysilane and hexamethyldisilazane as the surface treatment agent was 2: 5.
  • the reaction solution was filtered, the insolubles were washed with dichloromethane, and concentrated at 35 ° C. or less under reduced pressure.
  • Examples 1 to 21 and Comparative Examples 1 to 5 Among the components described in Tables 1 to 3, the components other than the filler (d), the filler (e) and the filler (i) (all in the form of powder) are After mixing at about 25 ° C. to obtain a uniform liquid component, the obtained liquid component and the powder components of filler (d), filler (e) and filler (i) are kneaded to obtain Example 1 A self-adhesive dental composite resin of ⁇ 21 and a dental composite resin (paste) of Comparative Examples 1 to 5 were prepared. Then, using these pastes, surface hardness, sag, tensile bond strength to dentin, bending strength, and discharge property were evaluated according to the method described later. Tables 1 to 3 show the compounding ratio (parts by mass) of this dental composite resin and the test results.
  • the surface hardness (Vickers hardness) of the cured product is preferably 25 to 55 Hv, more preferably 30 to 50 Hv, and still more preferably 35 to 45 Hv.
  • the dental composite resin is allowed to stand for 4 weeks with a thermostat kept at 60 ° C.
  • the value measured by the above method was taken as the sag of the dental composite resin after 4 weeks at 60 ° C. 2.5 mm or less is preferable, as for the difference between the sag property immediately after preparation and the sag property after 60 degreeC 4 weeks, 2.3 mm or less is more preferable, and 2.2 mm or less is more preferable.
  • the paste of the dental composite resin of each prepared Example and comparative example was filled, and it covered with the release film (polyester).
  • a slide glass was placed on the release film and pressed to smooth the coated surface of the paste.
  • the paste is irradiated with light through the release film for 10 seconds using a visible light irradiator for dental polymerization (trade name: Pencure 2000, manufactured by Morita Co., Ltd.) to obtain a cured product.
  • a visible light irradiator for dental polymerization trade name: Pencure 2000, manufactured by Morita Co., Ltd.
  • the tensile bond strength of the adhesion test sample was measured using a precision universal testing machine (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation) with the crosshead speed set at 2 mm / min.
  • the tensile bond strength (MPa) was taken as The tensile bond strength passed 9.5 MPa or more.
  • the cured product after storage is used as a test sample sample under the conditions of a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min using a precision universal testing machine (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation)
  • the bending strength was measured, and the average value of the measured values of each sample was calculated to be the bending strength (MPa).
  • the bending strength passed 100 MPa or more.
  • the syringe was stood vertically and the crosshead equipped with a jig for compressive strength test was lowered at 4 mm / min to discharge the paste while applying a load, and the maximum load at that time was taken as the discharge force.
  • the ejection force was measured at 25 ° C. When the ejection force is less than 36 N, ejection is easy and the ejection performance is good, and when it is 36 N or more, ejection is possible, but the ejection performance is poor. That is, it evaluated as the discharge property of a paste according to the following evaluation criteria. :: 10 N or less :: 10 N or more to less than 36 N C: 36 N or more Furthermore, the operator can operate without stress.
  • the self-adhesive dental composite resin according to the present invention gave good results in all of the surface hardness, the dischargeability and the sagging of the paste. . Further, the difference between the sagging property immediately after preparation and the sagging property at 60 ° C. after 4 weeks was hardly changed to 2.3 mm or less. Furthermore, in each case, a tensile bond strength of 9.9 MPa or more and a strength of 101.5 MPa or more were developed with respect to dentin.
  • the dental composite resins of Comparative Examples 1, 2 and 5 in which the filler (d) having an isoelectric point of 6.0 or more was not blended had a low surface hardness and a large sag. Furthermore, the sag changed significantly after storage at 60 ° C. for 4 weeks. Moreover, in Comparative Examples 3 and 4 in which a large amount of filler (d) was blended, although there were no problems with surface hardness and sag, the dischargeability from the container was poor.
  • the self-adhesive dental composite resin of the present invention can be used by first forming a cavity, directly filling the self-adhesive dental composite resin therein, and photocuring it for treatment of dental defects and caries. .

Abstract

La présente invention concerne une résine composite dentaire autocollante qui peut être évacuée, permettant de remplir directement une cavité, présente une excellente résistance mécanique après polymérisation et durcissement par irradiation de lumière visible, et résiste à l'affaissement lorsqu'elle est utilisée dans la cavité buccale. La présente invention concerne une résine composite dentaire autocollante qui contient (a) un monomère polymérisable (méth)acrylique contenant un groupe acide, (b) un un monomère polymérisable (méth)acrylique polyfonctionnel sans groupe acide (c) un initiateur de photopolymérisation, (d) une charge ayant un point isoélectrique de 6,0 ou plus, et (e) une charge ayant un point isoélectrique inférieur à 6,0, la charge (e) étant traitée par un agent de traitement de surface et ayant une taille de particule moyenne de 0,001 à 50,0 µm, l'agent de traitement de surface contenant (A) un agent de couplage de silane de formule générale (1) et (B) un organosilazane de formule générale (2), et la teneur en charge (d) étant de 0,1 à 15 parties en masse pour 100 parties en masse totales de composants monomères polymérisables.
PCT/JP2018/048143 2017-12-27 2018-12-27 Résine composite dentaire autocollante WO2019131881A1 (fr)

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JP2021107353A (ja) * 2019-12-27 2021-07-29 クラレノリタケデンタル株式会社 歯科用接着材料キット
WO2023085201A1 (fr) * 2021-11-15 2023-05-19 株式会社トクヤマデンタル Composition dentaire durcissable

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JP2002541309A (ja) * 1999-04-09 2002-12-03 ロディア・シミ 特に歯科用印象を採るために使用可能な親水性シリコーンエラストマー物質
WO2008093596A1 (fr) * 2007-02-01 2008-08-07 Kuraray Medical Inc. Composition durcissable pour applications dentaires
JP2010047488A (ja) * 2008-08-19 2010-03-04 Tokuyama Dental Corp 歯科用接着性組成物
WO2014083842A1 (fr) * 2012-11-30 2014-06-05 クラレノリタケデンタル株式会社 Composition dentaire pouvant polymériser et résine composite dentaire pouvant fluer
WO2016152659A1 (fr) * 2015-03-20 2016-09-29 株式会社ジーシー Composition durcissable pour utilisation dentaire et procédé pour la préparer

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JPH02134307A (ja) * 1988-11-11 1990-05-23 Kuraray Co Ltd 歯科用修復材
JP2002541309A (ja) * 1999-04-09 2002-12-03 ロディア・シミ 特に歯科用印象を採るために使用可能な親水性シリコーンエラストマー物質
WO2008093596A1 (fr) * 2007-02-01 2008-08-07 Kuraray Medical Inc. Composition durcissable pour applications dentaires
JP2010047488A (ja) * 2008-08-19 2010-03-04 Tokuyama Dental Corp 歯科用接着性組成物
WO2014083842A1 (fr) * 2012-11-30 2014-06-05 クラレノリタケデンタル株式会社 Composition dentaire pouvant polymériser et résine composite dentaire pouvant fluer
WO2016152659A1 (fr) * 2015-03-20 2016-09-29 株式会社ジーシー Composition durcissable pour utilisation dentaire et procédé pour la préparer

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Publication number Priority date Publication date Assignee Title
JP2021107353A (ja) * 2019-12-27 2021-07-29 クラレノリタケデンタル株式会社 歯科用接着材料キット
JP7278941B2 (ja) 2019-12-27 2023-05-22 クラレノリタケデンタル株式会社 歯科用接着材料キット
WO2023085201A1 (fr) * 2021-11-15 2023-05-19 株式会社トクヤマデンタル Composition dentaire durcissable

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