WO2024253204A1 - 歯科用硬化性組成物 - Google Patents

歯科用硬化性組成物 Download PDF

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Publication number
WO2024253204A1
WO2024253204A1 PCT/JP2024/020946 JP2024020946W WO2024253204A1 WO 2024253204 A1 WO2024253204 A1 WO 2024253204A1 JP 2024020946 W JP2024020946 W JP 2024020946W WO 2024253204 A1 WO2024253204 A1 WO 2024253204A1
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group
meth
dental
viscosity
filler
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English (en)
French (fr)
Japanese (ja)
Inventor
謙介 安宅
大和 野尻
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Kuraray Noritake Dental Inc
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Kuraray Noritake Dental Inc
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Priority to JP2025526174A priority Critical patent/JPWO2024253204A1/ja
Priority to EP24819431.8A priority patent/EP4725470A1/en
Publication of WO2024253204A1 publication Critical patent/WO2024253204A1/ja
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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
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/61—Cationic, anionic or redox initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/76—Fillers comprising silicon-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass

Definitions

  • the present invention relates to a dental hardenable composition used in dental treatment for bonding dental prostheses such as crowns, inlays and bridges to teeth. More specifically, the present invention relates to a dental hardenable composition (preferably a dental cement) that has excellent fluidity when bonding a dental prosthesis to a tooth substance, and also has excellent removability when excess cement protruding from the margin is removed in a semi-hardened state by provisionally irradiating it with a light irradiator.
  • a dental hardenable composition preferably a dental cement
  • dental cements are used as materials for attaching dental prostheses such as crowns, inlays, and bridges to the missing tooth crowns.
  • Dental cements generally consist of a polymerizable monomer, a filler, and a polymerization initiator.
  • Excess cement When bonding a tooth and a dental prosthesis using dental cement, an excess amount of dental cement is applied to the inner wall of the dental prosthesis and pressed against the tooth. During this pressing operation, it is common to apply an excess amount of dental cement to prevent the dental prosthesis from coming off. Excess dental cement overflows from the junction between the tooth and the dental prosthesis. It is desirable to completely remove the overflowing dental cement (hereinafter referred to as "excess cement”), since it is not only unaesthetic, but also has the potential to damage the oral tissues as it hardens. Normally, this excess cement is removed using a dental probe or the like, but it is difficult to remove the excess cement with a dental probe if the excess cement is not completely hardened.
  • the excess cement is first hardened by irradiating it with light, and then removed.
  • the excess cement is completely cured, it will adhere to the tooth structure and become extremely difficult to remove. For this reason, in clinical settings such as dental clinics, excess cement is removed when it has hardened to a certain extent and has low fluidity (semi-cured state).
  • it is irradiated with light for several seconds (usually about 1 to 5 seconds). This light irradiation is referred to as "pre-irradiation" in this specification.
  • main irradiation After performing the temporary irradiation to remove excess cement, light is irradiated again to completely harden the cement in the fitting area. This is referred to as "main irradiation" in this specification.
  • the irradiation time for main irradiation is set according to the type of light source and light intensity of the light irradiator used, and is usually around 10 to 20 seconds.
  • dental cement it is desirable for dental cement to have high fluidity, because if the prosthesis floats during bonding and the compatibility between the crown and the prosthesis deteriorates, problems such as the prosthesis falling off after restoration and secondary caries may occur.
  • the dental cement that overflows from the fitting is highly fluid, the excess cement will spread thinly under its own weight. The spread excess cement will need to be removed over a larger area, and the thin parts of the excess cement will harden completely during the temporary irradiation, making it extremely difficult to remove. To prevent this, it is desirable for the excess cement to have high shape retention.
  • Patent Document 1 describes the use of a specific polymerization initiator system to obtain a dental hardenable composition that has excellent removability when removed in a semi-hardened state after a short tentative irradiation of 1 to 2 seconds with a light irradiator, and also has excellent mechanical properties immediately after main irradiation and one day later.
  • the dental cement described in Patent Document 2 is described as having a plastic flow distance of 2 mm or less before hardening, which allows the kneaded material to maintain its shape without dripping under its own weight, and is also excellent in terms of removing excess cement after hardening.
  • Patent Document 3 discloses a dental cement kit that allows the excess cement to be easily removed in one lump by setting the polymerization initiation time during contact between the pretreatment agent and dental cement within a certain range, thereby aligning the hardening properties of the contact area between the pretreatment agent and dental cement, i.e., the center of the excess cement, and the surface of the provisionally irradiated excess cement.
  • the dental cement described in Patent Document 2 is a glass ionomer cement composition for dental bonding that does not contain a photoinitiator, and does not improve the removability of excess cement when it is immediately removed by temporary irradiation.
  • the present invention aims to provide a dental hardenable composition that exhibits sufficient fluidity to prevent the prosthesis from floating up during bonding, and also has excellent removability of excess cement during temporary irradiation.
  • the inventors of the present invention have continued their intensive research to solve the above problems, and as a result have succeeded in obtaining a dental cement that combines the contradictory properties of high fluidity when bonding dental prostheses and easy removal of excess cement due to the high shape retention of the excess cement, by creating a composition that exhibits unique viscosity behavior in which the viscosity drops significantly when pressure is applied compared to when left at rest, and the reduced viscosity quickly recovers to the viscosity when left at rest due to stress relaxation. Based on these findings, the inventors of the present invention have conducted further research and have completed the present invention.
  • a composition comprising a polymerizable monomer (A), a filler (B) having an average particle size of 1 ⁇ m or more, a polymerization initiator (C), a polymerization accelerator (D), and a rheology modifier (E),
  • the polymerization initiator (C) contains a photopolymerization initiator (C-1), the viscosity is measured over time using a rotational rheometer for a total of three minutes at a shear rate of D1 (0.01 s ), for one minute at a shear rate of D2 (10 s ), and again at a shear rate of D1 for one minute;
  • the viscosity V1 at an initial shear rate of D1 (0.01 s ) is 10,000 Pa ⁇ s or more and less than 20,000 Pa ⁇ s;
  • the viscosity V2 at a shear rate D2 (10 s ) is 100 Pa ⁇ s or less
  • a dental hardenable composition wherein the time T
  • the polymerizable monomer (A) is, in a total of 100 parts by mass of the polymerizable monomer (A),
  • a composition comprising a first agent and a second agent,
  • the first agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization initiator (C-2)
  • the second agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization accelerator (D-2);
  • the dental hardenable composition according to [7], wherein the first agent and/or the second agent contains a rheology modifier (E).
  • the dental curable composition according to any one of [1] to [8], wherein the rheology control agent (E) contains inorganic fine particles (E-1) having an average particle size of less than 1 ⁇ m.
  • the dental hardenable composition that exhibits sufficient fluidity to prevent the prosthesis from floating up during bonding and has excellent removability of excess cement during temporary irradiation.
  • the dental hardenable composition that becomes the excess cement during bonding does not spread too thinly, and the excess hardened material can be instantly removed by pre-irradiation.
  • FIG. 1 is a schematic diagram showing a mode of use of the dental curable composition of the present invention.
  • FIG. 2 is a schematic diagram illustrating an example of a change in shear rate and a change in viscosity.
  • the dental curable composition of the present invention comprises a polymerizable monomer (A), a filler (B) having an average particle size of 1 ⁇ m or more, a polymerization initiator (C), a polymerization accelerator (D), and a rheology modifier (E),
  • the polymerization initiator (C) contains a photopolymerization initiator (C-1), the viscosity is measured over time using a rotational rheometer for a total of three minutes at a shear rate of D1 (0.01 s ), for one minute at a shear rate of D2 (10 s ), and again at a shear rate of D1 for one minute;
  • the viscosity V1 at an initial shear rate of D1 (0.01 s ) is 10,000 Pa ⁇ s or more and less than 20,000 Pa ⁇ s;
  • the viscosity V2 at a shear rate D2 (10 s ) is 100 Pa ⁇ s or less, The time T required for the viscosity V3 to reach
  • the viscosity is significantly reduced when pressure is applied compared to when left at rest, and the reduced viscosity is quickly restored to the viscosity when left at rest due to stress relaxation, thereby exhibiting a unique viscosity behavior.Although the reason why such excellent effects are exhibited, it is presumed that this is because the composition has been able to combine the following physical properties.
  • Dental cement having a viscosity V2 of 100 Pa ⁇ s or less at a shear rate D2 has a viscosity that is sufficiently reduced by the pressure generated when bonding a dental prosthesis to a tooth, so that the dental prosthesis does not float up and become poorly fitted.
  • the time T required for the viscosity V3 to increase to 10,000 Pa ⁇ s after switching the shear rate from D2 to D1 is less than 40 seconds, so the excess cement does not drip and spread under its own weight.
  • the excess cement hardens due to pre-irradiation and cannot be peeled off when the excess cement drips and spreads thinly.
  • a certain thickness is guaranteed for the surplus cement, and the surplus cement does not harden excessively during pre-irradiation and become difficult to remove.
  • a sufficient amount of unhardened dental cement 1 (dental curable composition) is injected into the back side (recess) of a dental prosthesis so as to bond the dental prosthesis to the back side (recess) as shown in Fig. 1A.
  • an excess of unhardened dental cement 1 (dental curable composition) is injected so that the dental prosthesis does not come off when the dental prosthesis is fitted to the patient's teeth.
  • a practitioner e.g., a dentist
  • the excess cement 2 is temporarily irradiated (usually for about 1 to 5 seconds) to harden it. As shown in FIGS. 1C and 1D, the hardened excess cement 2 is peeled off with a dental probe 3, and the peeled excess cement 2 is removed.
  • FIG. 1A which corresponds to a shear rate D1
  • no force is applied to the dental hardenable composition, so the dental hardenable composition has high shape retention and is in a state of low fluidity.
  • 1B which corresponds to a shear rate D2
  • a force is applied by the practitioner, including when the practitioner uses a dental instrument. This pressure causes the dental hardenable composition present between the dental prosthesis and the patient's tooth to become highly fluid.
  • the dental hardenable composition of the present invention exhibits a unique viscous behavior in which the viscosity is significantly reduced and the fluidity is improved when pressurized (when force is applied) compared to when the composition is left stationary (when no force is applied), and the reduced viscosity is quickly restored to the viscosity when the composition is left stationary due to stress relaxation.By adjusting the time it takes for the viscosity to change from a low viscosity state to a high viscosity state, the occurrence of a problem in which the hardened product generated by pre-irradiation becomes unable to be peeled off after spreading thinly when the dental hardenable composition has high fluidity is suppressed, and the excess portion can be easily removed, thereby achieving the effect of achieving both the high fluidity required when using the composition and the shape retention required when removing the excess portion.
  • Patent Document 3 In the prior art, there are technologies such as Patent Document 3 that focus on hardening properties, and although Patent Document 3 also makes it possible to remove excess cement, it did not consider the fluidity of dental cement when used alone. Therefore, the present invention not only changes the viscous behavior but also controls the time for the change, thereby enabling the excess to be instantly removed by temporary irradiation, thereby achieving both the ease of removal of the excess, which is necessary for dental applications, and fluidity, which was not known in the prior art.
  • the viscosity V1 at an initial shear rate D1 (0.01 s -1 ) is 10,000 Pa ⁇ s or more and less than 20,000 Pa ⁇ s.
  • the viscosity V1 is preferably 10,000 Pa ⁇ s or more, more preferably 10,500 Pa ⁇ s or more, and even more preferably 11,000 Pa ⁇ s or more.
  • the viscosity V1 is preferably 20,000 Pa ⁇ s or less, more preferably 19,500 Pa ⁇ s or less, and even more preferably 19,000 Pa ⁇ s or less.
  • a known rotational rheometer device for example, product name "AR2000" manufactured by TA Instruments Japan Co., Ltd.
  • AR2000 TA Instruments Japan Co., Ltd.
  • the viscosity V2 at a shear rate D2 (10 s ⁇ 1 ) during the time-dependent viscosity measurement over a total period of 3 minutes is preferably 99 Pa ⁇ s or less, more preferably 80 Pa ⁇ s or less, and even more preferably 70 Pa ⁇ s or less.
  • the time T required for the viscosity V3 to reach 10,000 Pa ⁇ s after the shear rate during the time-dependent viscosity measurement over a total period of 3 minutes is switched from D2 back to D1 is preferably 35 seconds or less, more preferably 30 seconds or less, and even more preferably 25 seconds or less.
  • a radical polymerizable monomer is preferably used as the polymerizable monomer (A) used in the dental curable composition of the present invention.
  • the radical polymerizable monomer in the polymerizable monomer (A) include (meth)acrylate polymerizable monomers, (meth)acrylamide polymerizable monomers, esters such as ⁇ -cyanoacrylic acid, (meth)acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives.
  • (meth)acrylate polymerizable monomers and (meth)acrylamide polymerizable monomers are preferred from the viewpoint of curability.
  • the polymerizable monomer (A) is roughly classified into polymerizable monomers (A-1) not having an acidic group and polymerizable monomers (A-2) having an acidic group.
  • the term "(meth)acrylic” is a general term for "methacrylic” and "acrylic.”
  • the dental curable composition of the present invention if the polymerizable monomer (A) is contained in an amount of 60% by mass or more based on the total amount (100% by mass) of the composition, the viscosity of the composition becomes significantly low, and it becomes difficult to adjust the fluidity of the composition to an appropriate range even if a rheology modifier (E) is added.
  • the polymerizable monomer (A) is contained in an amount of less than 10% by mass based on the total amount (100% by mass) of the composition, the viscosity of the composition becomes significantly high, and it becomes difficult to adjust the fluidity of the composition to an appropriate range even if a rheology modifier (E) is added.
  • the content of the polymerizable monomer (A) in the dental curable composition of the present invention is preferably 10% by mass or more and less than 60% by mass, more preferably 20% by mass or more and less than 50% by mass, and even more preferably 25% by mass or more and less than 45% by mass, based on 100% by mass of the total amount of the composition.
  • the polymerizable monomer (A-1) having no acidic group in the present invention is divided into a hydrophilic polymerizable monomer (A-1a) having no acidic group and having a solubility in water at 25° C. of 4.5 g/L or more, and a hydrophobic polymerizable monomer (A-1b) having no acidic group and having a solubility in water at 25° C. of less than 4.5 g/L.
  • Hydrophilic polymerizable monomer having no acidic group In the dental curable composition of the present invention, the polymerizable monomer (A) preferably contains less than 15 parts by mass of a hydrophilic polymerizable monomer (A-1a) having no acidic group (hereinafter, sometimes simply referred to as "hydrophilic polymerizable monomer (A-1a)").
  • the hydrophilic polymerizable monomer (A-1a) means a monomer having no acidic group and having a solubility of 4.5 g/L or more in water at 25°C.
  • the hydrophilic polymerizable monomer (A-1a) when the hydrophilic polymerizable monomer (A-1a) is contained in an amount of 15 parts by mass or more based on a total of 100 parts by mass of the polymerizable monomer (A), the hydrophilic interaction generated with the rheology modifier (E) becomes strong, making it difficult to adjust the fluidity with the rheology modifier (E). Therefore, the content of the hydrophilic polymerizable monomer (A-1a) in the dental curable composition of the present invention is preferably less than 15 parts by mass, more preferably less than 10 parts by mass, and even more preferably less than 5 parts by mass, in 100 parts by mass of the total of the polymerizable monomers (A). The content of the hydrophilic polymerizable monomer (A-1a) may be 0 parts by mass in 100 parts by mass of the total of the polymerizable monomers (A).
  • the hydrophilic polymerizable monomer (A-1a) improves the wettability of the dental hardenable composition to tooth structure.
  • a radical polymerizable monomer having no acidic group but a polymerizable group is preferred, and from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and/or a (meth)acrylamide group.
  • hydrophilic polymerizable monomer (A-1a) examples include hydrophilic (meth)acrylate-based monofunctional polymerizable monomers such as 2-hydroxyethyl methacrylate (commonly known as "HEMA"), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, and tetrahydrofurfuryl (meth)acrylate; triethylene glycol dimethacrylate (commonly known as "3G”), tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, 1,3-bis(methacryloyloxy)-2-propanol, 1,2 -Bis(3-methacryloyloxy-2-hydroxypropoxy)ethane (commonly
  • hydrophilic polymerizable monomers (A-1a) HEMA, 3G, and #801 are preferred from the viewpoints of wettability to tooth structure and hardening properties.
  • the hydrophilic polymerizable monomer (A-1a) may be used alone or in combination of two or more kinds.
  • the polymerizable monomer (A) preferably contains a hydrophobic polymerizable monomer (A-1b) having no acidic group (hereinafter, sometimes simply referred to as "hydrophobic polymerizable monomer (A-1b)").
  • the hydrophobic polymerizable monomer (A-1b) means a monomer having no acidic group and having a solubility in water at 25°C of less than 4.5 g/L.
  • hydrophobic polymerizable monomer (A-1b) a radical polymerizable monomer having no acidic group and a polymerizable group is preferable, and from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and/or a (meth)acrylamide group.
  • examples include crosslinkable polymerizable monomers such as hydrophobic aromatic compound-based bifunctional polymerizable monomers, hydrophobic aliphatic compound-based bifunctional polymerizable monomers, and hydrophobic trifunctional or higher polymerizable monomers.
  • hydrophobic monofunctional polymerizable monomers examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, p-cumyl-phenoxyethylene glycol (meth)acrylate, phenoxybenzyl (meth)acrylate, stearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.
  • benzyl methacrylate, isobornyl methacrylate, and p-cumyl-phenoxyethylene glycol methacrylate are preferred.
  • hydrophobic aromatic bifunctional polymerizable monomers examples include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 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)acryloyloxypenta ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl
  • 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane commonly known as "Bis-GMA”
  • 2,2-bis(4-methacryloyloxyethoxyphenyl)propane 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added is 2.6, commonly known as "D-2.6E”
  • aliphatic compound-based bifunctional polymerizable monomers include monoethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)di(meth)acrylate, etc.
  • NPG neopentyl glycol dimethacrylate
  • UDMA 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate
  • DD 1,10-decanediol dimethacrylate
  • 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate are preferred, with NPG, UDMA, and DD being more preferred.
  • trifunctional or higher polymerizable monomers examples include 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(meth)acrylate, and 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane.
  • N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.
  • hydrophobic polymerizable monomers (A-1b) from the viewpoints of the fluidity of the paste and the mechanical strength of the cured product, aromatic compound-based bifunctional polymerizable monomers and aliphatic compound-based bifunctional polymerizable monomers are preferred.
  • the above-mentioned hydrophobic polymerizable monomer (A-1b) may be used alone or in combination of two or more kinds.
  • the content of the hydrophobic polymerizable monomer (A-1b) in the dental hardenable composition of the present invention is excessive, the wettability of the dental hardenable composition to tooth structure may decrease, resulting in a decrease in adhesive strength. If the content is too small, the hydrophilic interaction between the polymerizable monomer and the filler may be strong, resulting in insufficient fluidity of the paste, and the mechanical strength of the hardened product may be insufficient.
  • the content of the hydrophobic polymerizable monomer (A-1b) in the dental curable composition of the present invention is preferably 55 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 85 parts by mass or more, particularly preferably 90 parts by mass or more, and may be 100 parts by mass, based on 100 parts by mass of the total of the polymerizable monomers (A).
  • the dental curable composition of the present invention may contain a polymerizable monomer (A-2) having an acidic group.
  • the polymerizable monomer (A-2) having an acidic group used in the present invention is preferably a radically polymerizable monomer having at least one acidic group and a polymerizable group, and from the viewpoint of adhesion, the acidic group is preferably an acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, or a sulfonic acid group.
  • the polymerizable group is preferably a (meth)acrylic group and/or a (meth)acrylamide group.
  • Polymerizable monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyethyl dihydrogen phosphate, 9-(meth)acryloyloxypropyl dihydrogen phosphate, 10-(meth)acryloyloxybutyl dihydrogen phosphate, 11-(meth)acryloyloxybutyl dihydrogen phosphate, 12-(meth)acryloyloxybutyl dihydrogen phosphate, 13-(meth)acryloyl
  • Examples include acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(2-bromoethyl) hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, 2-(meth)acryloyloxypropyl-(4-methoxyphenyl) hydrogen phosphate, and their acid chlorides, alkali metal salts, and amine salts.
  • polymerizable monomers having a pyrophosphate group examples include bis[2-(meth)acryloyloxyethyl]pyrophosphate, bis[4-(meth)acryloyloxybutyl]pyrophosphate, bis[6-(meth)acryloyloxyhexyl]pyrophosphate, bis[8-(meth)acryloyloxyoctyl]pyrophosphate, bis[10-(meth)acryloyloxydecyl]pyrophosphate, and their acid chlorides, alkali metal salts, and amine salts.
  • Polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphat
  • Examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.
  • polymerizable monomers having a carboxylic acid group examples include monofunctional (meth)acrylic acid esters having one carboxyl group or its acid anhydride group in the molecule, monofunctional (meth)acrylic acid esters having multiple carboxyl groups or their acid anhydride groups in the molecule, and acid chlorides, alkali metal salts, and ammonium salts of these.
  • Examples of monofunctional polymerizable monomers having one carboxyl group or its acid anhydride group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, Examples include acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(me
  • Examples of monofunctional polymerizable monomers having multiple carboxyl groups or their acid anhydride groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride ...
  • Examples include dibutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, 6-(meth)acryloyloxyethyl naphthalene-1,2,6-tricarboxylic anhydride, 6-(meth)acryloyloxyethyl naphthalene-2,3,6-tricarboxylic anhydride, 4-(meth)acryloyloxyethyl carbonylpropionoyl-1,8-naphthalic anhydride, and 4-(meth)acryloyloxyethyl naphthalene-1,8-tricarboxylic anhydride.
  • polymerizable monomers having a sulfonic acid group examples include 2-sulfoethyl (meth)acrylate and its acid chlorides, alkali metal salts, and ammonium salts.
  • polymerizable monomers (A-2) having an acidic group from the viewpoint of good adhesive strength when used in a dental curable composition, a polymerizable monomer having a phosphoric acid group or a polymerizable monomer having a carboxylic acid group is preferred, and 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, etc. are preferred.
  • the content of the polymerizable monomer (A-2) having an acidic group in the dental hardenable composition of the present invention is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and even more preferably 0 to 15 parts by mass, per 100 parts by mass of the total polymerizable monomer (A), from the viewpoint of adhesion to tooth structure.
  • the dental curable composition of the present invention is required to contain a filler (B) having an average particle size of 1 ⁇ m or more in order to increase the mechanical strength of the cured product.
  • a filler (B) having an average particle size of 1 ⁇ m or more in order to increase the mechanical strength of the cured product.
  • the filler (B) include inorganic fillers, organic fillers, and organic-inorganic composite fillers.
  • the inorganic filler components include various glasses (mainly composed of silica, and optionally containing oxides of heavy metals, boron, aluminum, etc.).
  • glass powders of general compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass); dental glass powders such as barium glass (GM27884, 8235, manufactured by SCHOTT, E-2000, E-3000, manufactured by ESSTECH), strontium borosilicate glass (E-4000, manufactured by ESSTECH), lanthanum glass ceramics (GM31684, manufactured by SCHOTT), and fluoroaluminosilicate glass (GM35429, G018-091, G018-117, manufactured by SCHOTT), various ceramics, composite oxides such as silica-titania and silica-zirconia, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, and
  • various glasses such as silica-titania and silica-zirconia, calcium fluoride having a core-shell structure and having its surface coated with silica, ytterbium fluoride having a core-shell structure and having its surface coated with silica, yttrium fluoride having a core-shell structure and having its surface coated with silica, calcium phosphate having a core-shell structure and having its surface coated with silica, barium sulfate having a core-shell structure and having its surface coated with silica, zirconium dioxide having a core-shell structure and having its surface coated with silica, titanium dioxide having a core-shell structure and having its surface coated with silica, and hydroxyapatite having a core-shell structure and having its surface coated with silica are preferred.
  • organic filler components include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc.
  • the organic-inorganic composite filler is obtained by adding a polymerizable monomer to the inorganic filler described above in advance, forming it into a paste, polymerizing it, and pulverizing it.
  • TMPT filler trimethylolpropane methacrylate and silica filler mixed, polymerized, and pulverized
  • TMPT filler trimethylolpropane methacrylate and silica filler mixed, polymerized, and pulverized
  • the shape of the filler (B) may be spherical or amorphous.
  • the filler (B) is preferably the irregular filler (B-2), and it is more preferable to use a spherical filler (B-1) and the irregular filler (B-2) in combination.
  • the spherical filler (B-1) is a filler in which particles observed within a unit field of view in a photograph of the filler taken with an electron microscope are rounded and have an average uniformity of 0.6 or more, calculated by dividing the particle diameter in a direction perpendicular to the maximum diameter by the maximum diameter.
  • the spherical filler (B-1) in the dental curable composition of the present invention preferably has an average uniformity of 0.7 or more, more preferably 0.8 or more, in view of superior sliding effect.
  • the spherical filler (B-1) is not particularly limited in terms of material, since its spherical shape exerts a slipping effect and reduces interference between filler particles.
  • An embodiment includes a dental hardenable composition in which the spherical filler (B-1) is an inorganic filler.
  • the spherical filler (B-1) used in the present invention does not necessarily have to be manufactured or obtained as a single particle, but may be obtained by mixing two or more fillers with different average particle sizes or components, so long as the average particle size of each is within the above range.
  • the irregular filler (B-2) used in the present invention is a filler in which, when a photograph of the filler is taken with an electron microscope, the particles observed within a unit field of view are not rounded, and the average uniformity, calculated by dividing the particle diameter in a direction perpendicular to the maximum diameter by the maximum diameter, is less than 0.6.
  • the irregular filler (B-2) does not necessarily have to be manufactured or obtained as a single particle, but may be obtained by mixing two or more fillers with different average particle sizes or components, as long as the average particle size of each is within the above range.
  • the average particle size of the filler (B) used in the present invention is 1.0 to 6.0 ⁇ m, and from the viewpoint of mechanical strength and coating thickness, 1.0 to 5.0 ⁇ m is more preferable, and 1.0 to 3.0 ⁇ m is even more preferable. If the average particle size exceeds 6.0 ⁇ m, the dispersibility of the amorphous filler in the dental hardenable composition deteriorates, making it impossible to prepare a uniform paste.
  • the content of the filler (B) in the dental curable composition of the present invention is preferably 50 to 2000 parts by mass per 100 parts by mass of the total of the polymerizable monomers (A), and from the viewpoint of superior effect, it is more preferable that it is 100 to 1500 parts by mass, and even more preferable that it is 150 to 1000 parts by mass.
  • the content of the filler (B) in the dental hardenable composition of the present invention is preferably 45 to 95 mass %, more preferably 55 to 92 mass %, and even more preferably 60 to 90 mass %, of the total amount (100 mass %) of the composition, in order to provide excellent shape retention when left stationary and excellent mechanical strength of the hardened product.
  • the average particle size of the filler (B) and the inorganic fine particles (E-1) in this specification can be determined by a laser diffraction scattering method.
  • the average particle size of the inorganic fine particles (E-1) can also be measured by observation with an electron microscope, as described later.
  • the average particle diameters of the filler (B) and the inorganic fine particles (E-1) can be measured on a volume basis using, for example, a laser diffraction particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium.
  • SALD-2300 manufactured by Shimadzu Corporation
  • the filler (B) in the present invention is preferably one whose surface has been treated with a hydrophobizing agent (x-1) for the purpose of improving dispersibility in the polymerizable monomer. Since the hydrophobizing-treated filler can weaken the hydrophilic interaction with the polymerizable monomer, the hydrophobizing agent (x-1) is not particularly limited, and any known surface treatment agent capable of imparting hydrophobicity can be used without any restrictions.
  • hydrophobic treatment agent (x-1) include silane coupling agents, titanate coupling agents, aluminate coupling agents, zirco-aluminate coupling agents, etc. Among these, treatment with a silane coupling agent is particularly preferred because it provides a high effect of the present invention.
  • the hydrophobizing agent (x-1) may be used alone or in combination of two or more. When two or more hydrophobizing agents (x-1) are used in combination, the surface treatment layer formed therefrom may be a surface treatment layer of a mixture of two or more surface treatment agents, or may be a surface treatment layer of a multi-layer structure in which a plurality of surface treatment layers are laminated.
  • the surface treatment method may be a known method without any particular limitation.
  • the silane coupling agent is not particularly limited as long as it can impart hydrophobicity, and any known silane coupling agent can be used, but in terms of the superior effect of the present invention, a silane coupling agent having a polymerizable group represented by the following general formula (1) is preferably used.
  • a silane coupling agent having a polymerizable group represented by the following general formula (1) By using a silane coupling agent having a polymerizable group represented by the following general formula (1), the dispersibility of the filler is improved, the fluidity of the paste is improved, and the mechanical strength of the cured product is improved by polymerization between the surface treatment layer of the filler and various polymerizable monomers.
  • Y-SiR n X (3-n) (1)
  • R represents a group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group
  • X represents a hydroxyl group or a hydrolyzable group
  • n represents an integer of 0, 1, or 2.
  • multiple Rs may be the same or different, and multiple Xs may be the same or different.
  • Y has there are no particular limitations on the type of polymerizable group that Y has, and examples include (meth)acryloyl groups, vinyl groups, mercapto groups, (meth)allyl groups, and epoxy groups. Among these, from the standpoint of mechanical strength, etc., (meth)acryloyl groups are preferred, and methacryloyl groups are more preferred.
  • Y is a monovalent organic group having a polymerizable group and the polymerizable group is bonded to an organic group
  • the polymerizable group may be bonded directly to the organic group or may be bonded via a divalent group containing a heteroatom such as an oxygen atom or a nitrogen atom.
  • Y may be a group in which a (meth)acryloyl group and an organic group are bonded via a divalent group containing an oxygen atom.
  • a part of Y may form a (meth)acryloyloxy group or a (meth)acrylamide group.
  • Y has the number of polymerizable groups that Y has, but 1 to 4 is preferred, 1 or 2 is more preferred, and 1 is even more preferred.
  • Y has multiple polymerizable groups, they may be the same as or different from each other.
  • Y may be only the polymerizable group, or may be a monovalent organic group having a polymerizable group.
  • the functional group and the organic group may be bonded directly or indirectly via a divalent group containing a heteroatom such as an oxygen atom or a nitrogen atom.
  • the organic group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 26 carbon atoms.
  • an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 3 to 11 carbon atoms is more preferred, and an alkyl group having 5 to 11 carbon atoms is even more preferred, because they further improve adhesion to both dental restorative materials and tooth structure.
  • Examples of the alkyl group having 5 to 11 carbon atoms include an n-pentyl group, an n-hexyl group, an n-octyl group, and an n-undecyl group, and the n-octyl group and the n-undecyl group are preferred.
  • Examples of Y include (meth)acryloyloxyalkyl groups such as (meth)acryloyloxymethyl, (meth)acryloyloxyethyl, and 3-(meth)acryloyloxypropyl; ⁇ -(meth)acrylamidopropyl, vinyl, (meth)allyl, and ⁇ -glycidoxypropyl groups, of which (meth)acryloyloxymethyl, (meth)acryloyloxyethyl, 3-(meth)acryloyloxypropyl, ⁇ -(meth)acryloyloxyoctyl, and ⁇ -(meth)acryloyloxyundecyl groups are preferred, and ⁇ -(meth)acryloyloxyoctyl and ⁇ -(meth)acryloyloxyundecyl groups are more preferred.
  • (meth)acryloyloxyalkyl groups such as (meth)acryloyloxymethyl, (meth)acryloy
  • alkyl group represented by R there are no particular limitations on the type of alkyl group represented by R, and examples include alkyl groups having 1 to 5 carbon atoms, more specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-pentyl groups.
  • aryl group represented by R there are no particular limitations on the type of aryl group represented by R, and examples include aryl groups having 6 to 10 carbon atoms, and more specifically, examples include phenyl groups and naphthyl groups.
  • aralkyl group represented by R There are no particular limitations on the type of aralkyl group represented by R, and examples include aralkyl groups having 7 to 12 carbon atoms, and more specifically, examples include benzyl groups.
  • R is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
  • the hydrolyzable group represented by X can be a group that can form a silanol group together with the silicon atom to which it is bonded by hydrolysis, and examples of such groups include an alkoxy group, an acyloxy group, a siloxy group, and a halogen atom.
  • alkoxy group examples include alkoxy groups having 1 to 5 carbon atoms, and more specifically, examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and n-pentyloxy groups.
  • acyloxy group examples include acyloxy groups having 1 to 5 carbon atoms, and more specific examples include formyloxy groups, acetoxy groups, n-propionyloxy groups, isopropionyloxy groups, n-butanoyloxy groups, and n-pentanoyloxy groups.
  • siloxy group there are no particular limitations on the type of siloxy group, and examples include trimethylsiloxy groups.
  • halogen atom there are no particular limitations on the type of halogen atom, and examples include chlorine atoms and bromine atoms.
  • X is preferably an alkoxy group, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group or an ethoxy group.
  • n represents an integer of 0 to 2, and from the viewpoint of the mechanical strength of the cured product of the dental hardenable composition, n is preferably 0 or 1.
  • n is 0 or 1
  • the multiple Xs may be the same or different
  • the multiple Rs may be the same or different.
  • silane coupling agent examples include (meth)acryloyloxymethyltrimethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, and 10-(meth)acryloyloxyde 11-(meth)acryloyloxyundecyltrimethoxysilane, 11-(meth)acryloyloxyundecy
  • silane coupling agents having a polymerizable group represented by the general formula (1) such as allylmethyldiethoxysilane, allyldimethylmonoethoxysilane, (meth)allyl group-containing silane compounds; and silane coupling agents not having a polymerizable group, such as hexaethyldisilazane, hexa-n-propyldisilazane, hexaisopropyldisilazane, 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, and 1,1,1,3,3-pentamethyldisilazane.
  • the silane coupling agent may be a hydrolysate and/or a condensate thereof.
  • the silane coupling agent may be used alone or in combination of two or more kinds.
  • the polymerization initiator (C) is classified into a photopolymerization initiator (C-1) and a chemical polymerization initiator (C-2).
  • a photopolymerization initiator (C-1) As the dental curable composition of the present invention, it is necessary to contain the photopolymerization initiator (C-1) as the polymerization initiator (C) because the excess portion can be immediately removed by provisional irradiation.
  • the polymerization initiator (C) only the photopolymerization initiator (C-1) may be used, or the photopolymerization initiator (C-1) and the chemical polymerization initiator (C-2) may be used in combination.
  • the type of the photopolymerization initiator (C-1) is not particularly limited, and any conventionally known photopolymerization initiator can be used without any limitation.
  • Examples of conventionally known photopolymerization initiators include ⁇ -diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and ⁇ -aminoacetophenones.
  • the photopolymerization initiator (C-1) for example, a triazine compound substituted with a trihalomethyl group, as described in JP-A-2014-111555, may be used.
  • ⁇ -diketones include camphorquinone (commonly known as "CQ”), benzil, and 2,3-pentanedione.
  • Ketals include benzyl dimethyl ketal and benzyl diethyl ketal.
  • Thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
  • (Bis)acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis(2,6-dimethylphenyl)phosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and water-soluble acylphosphine oxide compounds disclosed in
  • ⁇ -Aminoacetophenones include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-pentanone, and 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-pentanone.
  • the photopolymerization initiator (C-1) is preferably an ⁇ -diketone or an acylphosphine oxide, more preferably an ⁇ -diketone, and even more preferably camphorquinone.
  • the photopolymerization initiator (C-1) may be used alone or in combination of two or more kinds.
  • the content of the photopolymerization initiator (C-1) is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the total of the polymerizable monomers (A).
  • C-2 ⁇ Chemical Polymerization Initiator (C-2)>
  • chemical polymerization initiator (C-2) there is no particular limitation on the type of chemical polymerization initiator (C-2), and any conventionally known chemical polymerization initiator can be used without any limitation.
  • the dental curable composition of the present invention contains a chemical polymerization initiator (C-2)
  • the mechanical strength of the obtained cured product can be further improved.
  • the chemical polymerization initiator (C-2) preferably contains an organic peroxide and/or an inorganic peroxide.
  • Organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, and peroxydicarbonates. Among these, hydroperoxides and peroxyesters are preferred.
  • hydroperoxide examples include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.
  • any known peroxy ester can be used without any restrictions as long as it has an acyl group on one side of the peroxy group and a hydrocarbon group or a group similar thereto on the other side.
  • Specific examples include ⁇ , ⁇ -bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexan
  • t-butylperoxymaleic acid t-butylperoxy-3,5,5-trimethylhexanoate
  • t-butylperoxybenzoate t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, and t-butylperoxyacetate are preferred, with t-butylperoxybenzoate being more preferred.
  • ketone peroxides examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
  • the peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)butane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.
  • dialkyl peroxide examples include ⁇ , ⁇ -bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)3-hexyne.
  • the diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, and benzoyl peroxides.
  • peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(2-methoxybutyl) peroxydicarbonate, and di(3-methyl-3-methoxybutyl) peroxydicarbonate.
  • Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, among which peroxodisulfates are preferred in terms of reactivity.
  • Examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate, among which sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are preferred.
  • the chemical polymerization initiator (C-2) may be used alone or in combination of two or more kinds.
  • the content of the chemical polymerization initiator (C-2) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.025 to 5 parts by mass, per 100 parts by mass of the total of the polymerizable monomers (A) from the viewpoints of adhesive strength with the adherend and operating time. If the content is 0.001 part by mass or more, it is easy to obtain appropriate adhesion, and if it is 10 parts by mass or less, it is easy to maintain operating time.
  • the dental curable composition of the present invention may contain a polymerization accelerator (D).
  • the polymerization accelerator (D) is a compound that accelerates the reaction in combination with the above-mentioned polymerization initiator (C), and is classified into a photopolymerization accelerator (D-1) and a chemical polymerization accelerator (D-2).
  • the polymerization accelerator (D) may contain only one of the photopolymerization accelerator (D-1) or the chemical polymerization accelerator (D-2), or may contain both the photopolymerization accelerator (D-1) and the chemical polymerization accelerator (D-2).
  • Photopolymerization Accelerator (D-1) There is no particular limitation on the type of photopolymerization accelerator (D-1), and any conventionally known photopolymerization accelerator can be used without any limitation.
  • Examples of the photopolymerization accelerator (D-1) used in the dental curable composition of the present invention include aldehydes, thiol compounds, aminobenzoic acid ester compounds, and amine reducing agents.
  • Aldehydes include terephthalaldehyde and benzaldehyde derivatives.
  • Benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and p-n-octyloxybenzaldehyde.
  • Thiol compounds include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.
  • Aminobenzoic acid ester compounds include ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-[(meth)acryloyloxy]ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, and n-butyl 4-(N,N-dimethylamino)benzoate.
  • Amine reducing agents are broadly classified into aromatic amines and aliphatic amines, and either aromatic amines or aliphatic amines may be used in the present invention.
  • aromatic amine known aromatic secondary amines, aromatic tertiary amines, etc. may be used.
  • aromatic secondary amines or aromatic tertiary amines N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di ...
  • N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline.
  • Aliphatic amines include aliphatic primary amines such as n-butylamine, n-hexylamine, and n-octylamine; aliphatic secondary amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and aliphatic tertiary amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine.
  • aliphatic primary amines such as n-butylamine, n-hexylamine, and n-oc
  • photopolymerization accelerators from the viewpoints of curability and storage stability, aminobenzoic acid ester compounds and aliphatic tertiary amines are preferred, and ethyl 4-(N,N-dimethylamino)benzoate, N-methyldiethanolamine and triethanolamine are more preferred.
  • the above-mentioned photopolymerization accelerator (D-1) may be used alone or in combination of two or more kinds.
  • the content of the photopolymerization accelerator (D-1) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the polymerizable monomers (A). If the content is 0.01 parts by mass or more, it is easy to obtain suitable adhesion, and if it is 10 parts by mass or less, it is easy to ensure sufficient operating time.
  • the dental hardenable composition includes a dental hardenable composition in which the polymerization accelerator (D) includes a chemical polymerization accelerator (D-2).
  • the chemical polymerization accelerator (D-2) used in the dental curable composition of the present invention is roughly classified into a chemical polymerization accelerator (D-2a) (hereinafter, sometimes simply referred to as "chemical polymerization accelerator (D-2a)”) that is suitably used when the polymerizable monomer (A) does not contain a polymerizable monomer (A-2) having an acidic group, and a chemical polymerization accelerator (D-2b) (hereinafter, sometimes simply referred to as "chemical polymerization accelerator (D-2b)”) that is suitably used when the polymerizable monomer (A) contains a polymerizable monomer (A-2) having an acidic group.
  • D-2a chemical polymerization accelerator
  • D-2b chemical polymerization accelerator
  • the chemical polymerization accelerator (D-2) can be selected depending on the type of polymerizable monomer. Either one of the chemical polymerization accelerator (D-2a) which is preferably used when the polymerizable monomer (A-2) having an acidic group is not contained, or the chemical polymerization accelerator (D-2b) which is preferably used when the polymerizable monomer (A-2) having an acidic group is contained, may be contained, or both may be contained.
  • the copper compound can be suitably used in both cases where the polymerizable monomer (A) contains a polymerizable monomer (A-2) having an acidic group and where the polymerizable monomer (A) does not contain a polymerizable monomer (A-2) having an acidic group, and therefore is exemplified as both the chemical polymerization accelerator (D-2a) and the chemical polymerization accelerator (D-2b).
  • Chemical polymerization accelerator (D-2a) examples include aromatic amines having no electron-withdrawing group in the aromatic ring, 4th period transition metal compounds, transition metal compounds other than the 4th period transition metal compounds, and thiourea compounds, and specific examples thereof include the following.
  • Examples of such compounds include aniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline.
  • the fourth period transition metal compound may be any of vanadium compounds, copper compounds, and compounds of fourth period transition metals other than vanadium and copper.
  • the chemical polymerization accelerator (D-2a) is preferably a vanadium compound or a copper compound from the viewpoint of the polymerization acceleration effect.
  • vanadium compounds include vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis(maltolato)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V)oxytriisopropoxide, ammonium metavanadate(V), sodium metavanadate(V), vanadium pentoxide(V), divanadium tetroxide(IV) and vanadyl sulfate(IV).
  • vanadyl acetylacetonate and bis(maltolato)oxovanadium(IV) are preferred from the viewpoint of solubility in solvents, with vanadyl acetylacetonate and bis(maltolato)oxovanadium(IV) being more preferred.
  • the copper compound is preferably a compound that is soluble in the radical polymerizable monomer.
  • copper compounds include copper(II) carboxylates (e.g., copper(II) acetate, copper(II) benzoate, copper(II) isobutyrate, copper(II) gluconate, copper(II) citrate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octylate, copper(II) octenoate, copper(II) naphthenate, copper(II) acrylate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate); ⁇ -diketone copper (e.g., copper(II) acetylacetone, copper(II) trifluoroacetylacetone, copper(II) hexafluoroacetylacetone, and 2,2,6,6-te
  • copper(II) carboxylate, copper(II) ⁇ -diketone, and copper(II) ⁇ -ketoester are preferred, and copper(II) acetate and copper(II) acetylacetonate are more preferred.
  • fourth-period transition metal compounds include scandium isopropoxide, iron(III) ethoxide, titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, titanium hydroxide, and titanium fluoride.
  • vanadyl acetylacetonate (IV) and bis(maltolate)oxovanadium (IV) are preferred, with vanadyl acetylacetonate (IV) being more preferred, from the viewpoint of their high polymerization promoting effect.
  • transition metal compounds other than those in the fourth period include strontium carbonate, strontium hydroxide, strontium ethoxide, tin(II) methoxide, indium ethoxide, actinium ethoxide, yttrium isopropoxide, lanthanum methoxide, lanthanum ethoxide, lanthanum isopropoxide, lanthanum butoxide, lanthanum hydroxide, lanthanum carbonate, lanthanum fluoride, cerium isopropoxide, praseodymium isopropoxide, promethium isopropoxide, neodymium isopropoxide, and samarium.
  • Examples include marium isopropoxide, europium isopropoxide, gadolinium isopropoxide, terbium ethoxide, terbium methoxide, dysprosium isopropoxide, holmium isopropoxide, erbium isopropoxide, thulium isopropoxide, ytterbium isopropoxide, zirconium ethoxide, zirconium isopropoxide, zirconium butoxide, tungsten (IV) methoxide, tungsten (IV) isopropoxide, and tungsten (IV) butoxide.
  • thiourea compound examples include thiourea, methylthiourea, ethylthiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1-(2-pyridyl)-2-thiourea, (6-methyl-pyridin-2-yl)thiourea, 4,4-dimethylethylenethiourea, etc.
  • 1-(2-pyridyl)-2-thiourea, (6-methyl-pyridin-2-yl)thiourea, and 4,4-dimethylethylenethiourea are preferred from the viewpoints of solubility in a solvent and storage stability.
  • the above-mentioned chemical polymerization accelerator (D-2a) may be used alone or in combination of two or more kinds.
  • the content of the chemical polymerization accelerator (D-2a) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.025 to 5 parts by mass, per 100 parts by mass of the total of the polymerizable monomers (A).
  • Chemical polymerization accelerator (D-2b) examples include copper compounds, aromatic sulfinic acids and their salts, benzotriazole compounds, benzimidazole compounds, bromides, and sulfur-containing reducing inorganic compounds. Specific examples thereof include the following.
  • the copper compound is preferably a compound that is soluble in the polymerizable monomer component.
  • Specific examples thereof include copper(II) carboxylates (e.g., copper(II) acetate, copper(II) benzoate, copper(II) isobutyrate, copper(II) gluconate, copper(II) citrate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octylate, copper(II) octenoate, copper(II) naphthenate, copper(II) acrylate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate); ⁇ -diketone copper (e.g., copper(II) acetylacetone, copper(II) trifluoroacetylacetone, copper(II) hexafluoroacetylacetone, and 2,2,6,6-t
  • copper(II) carboxylate, copper(II) ⁇ -diketone, and copper(II) ⁇ -ketoester are preferred, and copper(II) acetate and copper(II) acetylacetonate are more preferred.
  • Aromatic sulfinic acids and their salts include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, naphthalenesulfinic acid, and their lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, iron, zinc, ammonium, tetramethylammonium, and tetraethylammonium salts.
  • the lithium, sodium, potassium, magnesium, and calcium salts of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are preferred, and the lithium, sodium, potassium, magnesium, and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.
  • the aromatic sulfinic acid and its salt are at least partially dispersed in the composition in the form of a powder.
  • the dental hardenable composition of the present invention can ensure a longer operation time, and when applied to a wet body such as a tooth, the aromatic sulfinic acid and its salt dissolve in water on the surface of the wet body, thereby further enhancing the polymerizability at the adhesive interface and inside the resin-impregnated layer.
  • the aromatic sulfinic acid and its salt When the aromatic sulfinic acid and its salt are dispersed in the form of a powder, it is preferable that the aromatic sulfinic acid and its salt have a solubility in water at room temperature (25°C) of 1 mg/100 mL or more.
  • the solubility of 1 mg/100 mL or more when the dental hardenable composition of the present invention is applied to a wet body, the aromatic sulfinic acid and its salt are easily dissolved sufficiently in the water of the wet body at the adhesive interface, and as a result, the effect of dispersing in the form of a powder is easily manifested.
  • the average particle size is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the average particle size is preferably 0.01 ⁇ m or more.
  • the average particle size is preferably in the range of 0.01 to 500 ⁇ m, and more preferably in the range of 0.01 to 100 ⁇ m.
  • the average particle size can be measured in the same manner as the average particle size of the filler (B) described above.
  • aromatic sulfinic acids and their salts are dispersed as powders
  • various shapes can be used, such as spherical, needle-like, plate-like, and crushed, but there are no particular limitations.
  • Fine powders of aromatic sulfinic acid salts can be produced by conventional methods such as pulverization and freeze-drying.
  • the content of aromatic sulfinic acid and its salt is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total of polymerizable monomers (A) in the adhesive composition of the present invention. If the content is less than 0.1 part by mass, adhesion may decrease, and if it exceeds 5 parts by mass, operating time may become shorter.
  • the benzotriazole compound and the benzimidazole compound are represented by the following general formulas (2) and (3), respectively.
  • R 1 to R 8 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an aralkyl group, or a halogen atom.
  • the alkyl groups represented by R 1 to R 8 may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a cyclohexyl group, an n-heptyl group, a cycloheptanyl group, an n-octyl group, a 2-ethy
  • the aryl group represented by R 1 to R 8 preferably has a carbon number of 6 to 10.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.
  • the alkoxy groups represented by R 1 to R 8 may be linear, branched, or cyclic, and preferably have a carbon number of 1 to 8.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-octyloxy group, and a 2-ethylhexyloxy group.
  • the alkenyl groups represented by R 1 to R 8 may be linear, branched, or cyclic, and preferably have a carbon number of 1 to 6.
  • Examples of the alkenyl group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • the aralkyl group represented by R 1 to R 8 is preferably an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (particularly an aryl group having 6 to 10 carbon atoms), such as a benzyl group.
  • Examples of the halogen atom represented by R 1 to R 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 to R 8 are preferably a hydrogen atom or a methyl group.
  • the benzotriazole compounds and benzimidazole compounds may be used alone or in combination.
  • Examples of the benzotriazole compounds and benzimidazole compounds include 1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, and 5,6-dimethylbenzimidazole.
  • 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferred from the viewpoint of operating time margin.
  • Bromides include zinc bromide, potassium bromide, sodium bromide, calcium bromide, indium bromide, ammonium bromide, and tetrabutylammonium bromide. Of these, zinc bromide, ammonium bromide, and tetrabutylammonium bromide are particularly preferred.
  • Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites, with sulfites and bisulfites being preferred.
  • Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite.
  • the dental hardenable composition of the present invention can ensure a longer operation time, and when applied to a tooth, the sulfur-containing reducing inorganic compound dissolves in water on the surface of the tooth, so that the polymerizability at the adhesive interface and inside the resin-impregnated layer can be further increased.
  • the sulfur-containing reducing inorganic compound preferably has a solubility in water at room temperature (25°C) of 1 mg/100 mL or more.
  • the sulfur-containing reducing inorganic compound By having a solubility of 1 mg/100 mL or more, when the dental hardenable composition of the present invention is applied to a tooth, the sulfur-containing reducing inorganic compound is easily dissolved in water at the adhesive interface, and as a result, the effect of dispersing in the form of a powder is easily achieved.
  • the sulfur-containing reducing inorganic compound preferably has an average particle size of 500 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less, from the viewpoint of making it difficult to settle.
  • the average particle size is preferably 0.01 ⁇ m or more.
  • the average particle size when dispersed as a powder, is preferably in the range of 0.01 to 500 ⁇ m, and more preferably in the range of 0.01 to 100 ⁇ m.
  • the average particle size can be measured in the same manner as the average particle size of the filler (B) described above.
  • sulfur-containing reducing inorganic compound When the sulfur-containing reducing inorganic compound is dispersed in powder form, various shapes can be used, such as spherical, needle-like, plate-like, and crushed, but there are no particular limitations.
  • the sulfur-containing reducing inorganic compound can be made into a fine powder by conventional methods such as pulverization and freeze-drying.
  • the above-mentioned chemical polymerization accelerator (D-2b) may be used alone or in combination of two or more types.
  • the content of the chemical polymerization accelerator (D-2b) is preferably 0.001 to 40 parts by mass, more preferably 0.005 to 20 parts by mass, and even more preferably 0.025 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable monomers (A).
  • the dental hardenable composition of the present invention contains a chemical polymerization initiator (C-2) and a chemical polymerization accelerator (D-2), from the viewpoint of storage stability, it is preferable to package the dental hardenable composition into two or more components so that the components of the composition do not react before use. In this case, it is preferable to mix the chemical polymerization initiator (C-2) in a component different from the thiourea compound or aromatic sulfinic acid and its salt.
  • the polymerizable monomer (A) and the filler (B) are mixed into both the first and second components to make it a two-paste type.
  • the composition comprises a first agent and a second agent
  • the first agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization initiator (C-2)
  • the second agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization accelerator (D-2);
  • the dental hardenable composition may include a dental hardenable composition in which the first agent and/or the second agent contains a rheology modifier (E).
  • the rheology modifier (E) may be contained only in the first agent, or only in the second agent. From the viewpoint of the storage stability of each of the first agent and the second agent, it is preferable that the rheology modifier (E) is contained in both the first agent and the second agent.
  • the dental hardenable composition of the present invention needs to contain a rheology adjuster (E) in order to achieve both the fluidity of the paste, excellent shape retention of the excess cement, and easy removal of the excess cement by provisional irradiation.
  • the rheology modifier (E) refers to a component capable of changing the viscoelasticity of the dental hardenable composition. By blending the rheology modifier (E), the viscosity of the dental hardenable composition can be changed so that the viscosity is lowered from the viscosity at rest when pressure is applied, and the viscosity behavior can be changed so that the viscosity returns to the viscosity at rest when the pressure is released.
  • Examples of the rheology modifier (E) include inorganic fine particles (E-1) having an average particle size of less than 1 ⁇ m (hereinafter referred to as inorganic fine particles (E-1)), a (meth)acrylic compound (E-2) having a weight average molecular weight of 1,000 to 80,000 and a weight average molecular weight per polymerizable group of 1,250 or more and less than 20,000 (hereinafter referred to as (meth)acrylic compound (E-2)), a hydrophilic polymer (E-3), and cellulose nanofibers.
  • the rheology control agent (E) is other than that contained in the filler (B).
  • the inorganic fine particles (E-1) may include various glasses (mainly composed of silica, and optionally containing oxides of heavy metals, boron, aluminum, etc.).
  • glasses mainly composed of silica, and optionally containing oxides of heavy metals, boron, aluminum, etc.
  • glass powders of general compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass); dental glass powders such as barium glass (GM27884, 8235, manufactured by SCHOTT, E-2000, E-3000, manufactured by ESSTECH), strontium borosilicate glass (E-4000, manufactured by ESSTECH), lanthanum glass ceramics (GM31684, manufactured by SCHOTT), and fluoroaluminosilicate glass (GM35429, G018-091, G018-117, manufactured by SCHOTT), various ceramics, composite oxides such as silica-titania and si
  • various glasses such as silica-titania and silica-zirconia, calcium fluoride having a core-shell structure and having its surface coated with silica, ytterbium fluoride having a core-shell structure and having its surface coated with silica, yttrium fluoride having a core-shell structure and having its surface coated with silica, calcium phosphate having a core-shell structure and having its surface coated with silica, barium sulfate having a core-shell structure and having its surface coated with silica, zirconium dioxide having a core-shell structure and having its surface coated with silica, titanium dioxide having a core-shell structure and having its surface coated with silica, and hydroxyapatite having a core-shell structure and having its surface coated with silica are preferred.
  • the inorganic fine particles (E-1) used in the present invention have an average particle size of less than 1 ⁇ m.
  • the average particle size is preferably 0.001 to 0.5 ⁇ m, and more preferably 0.01 to 0.3 ⁇ m.
  • the rheology control agent (E) includes inorganic fine particles (E-1) having an average particle size of less than 1 ⁇ m.
  • Another preferred embodiment of the dental hardenable composition includes the inorganic fine particles (E-1) having an average particle size of 7 to 200 nm.
  • the average particle size of the inorganic fine particles (E-1) may be 100 nm or less, since specific viscosity behavior is easily obtained.
  • the average particle size of the rheology control agent (E) can be measured by a laser diffraction scattering method or by observation with an electron microscope.
  • the laser diffraction scattering method is as described above.
  • the electron microscope observation can be performed, for example, by taking a photograph of the particles with an electron microscope (S-4000 model, manufactured by Hitachi, Ltd.) and measuring the particle diameters of particles (200 or more) observed within a unit field of view of the photograph using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountec Co., Ltd.)).
  • the particle diameter is determined as the 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 their particle diameters.
  • the shape of the inorganic fine particles (E-1) may be spherical or amorphous.
  • the inorganic fine particles (E-1) include spherical inorganic fine particles (E-1a), and it is more preferable to use the spherical inorganic fine particles (E-1a) in combination with amorphous inorganic fine particles (E-1b).
  • Spherical inorganic fine particles (E-1a) are particles that are observed within a unit field of view of a photograph of the filler taken with an electron microscope and are rounded, and the particle diameter in the direction perpendicular to the maximum diameter is the maximum diameter.
  • the average uniformity of the divided filler is 0.6 or more.
  • the spherical inorganic fine particles (E-1a) in the dental curable composition of the present invention preferably have an average uniformity of 0.7 or more, and more preferably 0.5 or more, in view of the excellent sliding effect that occurs when an external force is applied. It is more preferable that the number is 8 or more.
  • the spherical inorganic fine particles (E-1a) have a spherical shape, which provides a slipping effect when an external force is applied thereto, and can reduce interference between the filler particles, thereby providing fluidity to the paste when an external force is applied thereto.
  • the material of the filler is not particularly limited.
  • the dental hardenable composition includes the spherical inorganic fine particles (E-1a) as an inorganic filler.
  • Another preferred embodiment of the dental hardenable composition includes a dental hardenable composition in which the spherical inorganic fine particles (E-1a) are spherical nanosilica.
  • the perfect sphericity preferably has an average uniformity of 0.9 or more, and more preferably 0.95 or more.
  • the silanol groups on the particle surface of the silica form a crosslinked structure through hydrogen bonding, and in addition, the silica exerts a slip effect, making it easier to obtain the required specific viscous behavior, and the time T required for the viscosity V3 to reach 10,000 Pa s after the shear rate is switched from D2 back to D1 can be made shorter.
  • the spherical inorganic fine particles (E-1a) used in the present invention do not necessarily have to be manufactured or obtained as single particles, but may be obtained by mixing two or more fillers with different average particle sizes or components, so long as the average particle size of each is within the above range.
  • the amorphous inorganic fine particles (E-1b) used in the present invention are particles that are not rounded and have a diameter perpendicular to the maximum diameter when observed within a unit field of view of a filler photographed with an electron microscope.
  • the filler has an average uniformity of less than 0.6, calculated by dividing the particle diameter by the maximum diameter.
  • the amorphous inorganic fine particles (E-1b) do not necessarily have to be manufactured or obtained as single particles, but may be obtained by mixing two or more fillers with different average particle sizes or components, so long as the average particle size of each is within the above range.
  • the content of inorganic fine particles (E-1) in the dental curable composition of the present invention is preferably 0.1 to 200 parts by mass per 100 parts by mass of the total of polymerizable monomers (A), and is more preferably 0.5 to 100 parts by mass, and even more preferably 1 to 50 parts by mass, from the viewpoints of the effects of being able to shorten the time until the reduced viscosity is quickly restored to the viscosity when left at rest due to stress relaxation, and of being more excellent in fluidity when the paste is pressurized.
  • the content of inorganic fine particles (E-1) in the dental curable composition of the present invention is preferably 0.1 to 50 mass% out of the total amount of the composition (100 mass%) in terms of excellent shape retention when left to stand and mechanical strength of the cured product, and is more preferably 0.2 to 30 mass%, and even more preferably 1 to 10 mass%, in terms of excellent effects such as shortening the time until the reduced viscosity is quickly restored to the viscosity when left to stand due to stress relaxation and excellent fluidity when the paste is pressurized.
  • the inorganic fine particles (E-1) in the present invention may be those whose surfaces have been treated with a hydrophobizing agent (x-1) for the purpose of improving dispersibility in a polymerizable monomer. Since the inorganic fine particles are hydrophobized and can weaken the hydrophilic interaction with the polymerizable monomer, the hydrophobizing agent (x-1) is not particularly limited, and any known surface treatment agent capable of imparting hydrophobicity may be used without any restrictions. As the hydrophobizing agent (x-1) used for the hydrophobizing treatment of the inorganic fine particles (E-1), the same hydrophobizing agent (x-1) as that for the filler (B) can be used.
  • the dental curable composition contains a filler (B) and inorganic fine particles (E-1), and both the filler (B) and the inorganic fine particles (E-1) have been hydrophobized
  • the hydrophobization treatment agent (x-1) used for the hydrophobization treatment of the inorganic fine particles (E-1) and the hydrophobization treatment agent (x-1) used for the hydrophobization treatment of the filler (B) may be the same as or different from each other.
  • the blending ratio of the filler (B) to the inorganic fine particles (E-1) is preferably 100:0.1 to 100:50, more preferably 100:0.15 to 100:25, and even more preferably 100:0.2 to 100:15.
  • the content of the rheology modifier (E) can be appropriately changed depending on the type of material within the range in which the effects of the present invention are achieved.
  • the blending ratio of the filler (B) to the amorphous inorganic fine particles (E-1b) may be within a range of 100:0.2 to 100:10, or may be within a range of 100:0.5 to 100:8.
  • the (meth)acrylic compound (E-2) can be roughly classified into two types: urethane-modified (meth)acrylic compounds (E-2a) and (meth)acrylic compounds having no urethane skeleton (E-2b).
  • the urethane-modified (meth)acrylic compound (E-2a) is preferred in terms of the ease of introduction of a (meth)acrylic group, the specific viscosity behavior in which the viscosity is significantly reduced when pressurized compared to when left at rest and the reduced viscosity is rapidly restored to the viscosity when left at rest due to stress relaxation, and the effect of reducing polymerization shrinkage stress.
  • the urethane-modified (meth)acrylic compound (E-2a) can be easily synthesized, for example, by addition reaction of a polyol containing a polymer skeleton described below, a compound having an isocyanate group (-NCO), and a (meth)acrylic compound having a hydroxyl group (-OH).
  • the urethane-modified (meth)acrylic compound (E-2a) can also be easily synthesized by ring-opening addition reaction of a (meth)acrylic compound having a hydroxyl group with a lactone or an alkylene oxide, and then addition reaction of the resulting compound having a hydroxyl group at one end with a compound having an isocyanate group.
  • the (meth)acrylic compound (E-2b) having no urethane skeleton can be obtained, for example, by subjecting a polymer of a monomer having a hydroxyl group to a dehydration condensation reaction with (meth)acrylic acid.
  • a (meth)acrylic compound having a weight average molecular weight of 1,000 to 80,000 and a weight average molecular weight per polymerizable group of 1,250 or more and less than 20,000 is regarded as a (meth)acrylic compound (E-2) regardless of its solubility in water at 25°C.
  • the urethanized (meth)acrylic compound (E-2a) is preferably a (meth)acrylate having, in addition to a urethane bond, a structure (polymer skeleton) selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyethers, polyconjugated dienes, and hydrogenated polyconjugated dienes, and more preferably a (meth)acrylate having at least one polyol moiety selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyethers, polyconjugated dienes, and hydrogenated polyconjugated dienes having a structure derived from an aliphatic diol unit having 4 to 18 carbon atoms and a branched structure in one molecule.
  • examples of the polyester include copolymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 18 carbon atoms, copolymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 18 carbon atoms, ⁇ -propiolactone polymers, ⁇ -butyrolactone polymers, ⁇ -valerolactone polymers, ⁇ -caprolactone polymers, and copolymers thereof.
  • dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid
  • copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as
  • copolymers of dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 12 carbon atoms
  • copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid
  • aliphatic diols having 2 to 12 carbon atoms are preferred.
  • polycarbonate examples include polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms and bisphenol A. Of these, polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms and bisphenol A are preferred.
  • polyurethane examples include polymers of aliphatic diols having 2 to 18 carbon atoms and diisocyanates having 1 to 18 carbon atoms, and polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms are preferred.
  • polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(1-methylbutylene glycol).
  • polyconjugated dienes and hydrogenated polyconjugated dienes examples include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof.
  • the structures of polyester, polycarbonate, and polyconjugated diene are preferred in terms of excellent mechanical strength and water resistance.
  • a polyol having the above-mentioned polymer skeleton can be used.
  • Examples of compounds having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMHMDI), tricyclodecane diisocyanate (TCDDI), and adamantane diisocyanate (ADI).
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • XDI xylylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • THMDI trimethylhexamethylene diisocyanate
  • TDDI tricyclodecane diisocyanate
  • ADI adamantane diisocyanate
  • Examples of (meth)acrylic compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin mono(meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate.
  • Hydroxy(meth)acrylate compounds such as 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri(meth)acrylate, and dipentaerythritol tri- or tetra(meth)acrylate; hydroxy(meth)acrylamide compounds such as N-hydroxyethyl(meth)acrylamide, and N,N-bis(2-hydroxyethyl)(meth)acrylamide.
  • Examples of the aliphatic diols having 4 to 18 carbon atoms and a branched structure include 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 2-methyl-1,10-decanediol, 2,9-dimethyl-1,10-decanediol, 2-methyl-1,11-undecanediol, and 2-methyl-1,12-undecanediol.
  • dimethyl-1,15-pentadecanediol examples include 2,14-dimethyl-1,15-pentadecanediol, 2,14-dimethyl-1,15-pentadecanediol, 2-methyl-1,16-hexadecanediol, and 2,15-dimethyl-1,16-hexadecanediol.
  • an aliphatic diol having 5 to 12 carbon atoms and a methyl group as a side chain such as 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, or 2,8-dimethyl-1,9-nonanediol, as the polyol component, more preferably 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, or 2,7-dimethyl-1,8-octanediol, and even more preferably 3-methyl-1,5-pentanediol or 2-methyl-1
  • the resulting urethane-modified (meth)acrylic compound (E-2a) may be any combination of a polyol having at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, a compound having an isocyanate group, and a (meth)acrylic compound having a hydroxyl group.
  • the (meth)acrylic compound (E-2b) having no urethane skeleton preferably has a structure (polymer skeleton) selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene.
  • examples of the polyester include copolymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 18 carbon atoms, copolymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 18 carbon atoms, ⁇ -propiolactone polymers, ⁇ -butyrolactone polymers, ⁇ -valerolactone polymers, ⁇ -caprolactone polymers, and copolymers thereof.
  • dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid
  • copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as
  • copolymers of dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 12 carbon atoms
  • copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid
  • aliphatic diols having 2 to 12 carbon atoms are preferred.
  • polycarbonate examples include polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms and bisphenol A. Of these, polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms and bisphenol A are preferred.
  • polyurethane examples include polymers of aliphatic diols having 2 to 18 carbon atoms and diisocyanates having 1 to 18 carbon atoms, and polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms are preferred.
  • polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(1-methylbutylene glycol).
  • polyconjugated dienes and hydrogenated polyconjugated dienes examples include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof.
  • the structures of polyester, polycarbonate, and polyconjugated diene are preferred in terms of excellent flexibility and water resistance.
  • the above-mentioned polyol having a polymer skeleton can be used.
  • the glass transition temperature and acetone solubility of the (meth)acrylic compound (E-2b) having no urethane skeleton can be adjusted by adjusting the skeleton and molecular weight of the structure (polymer skeleton) selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene.
  • Examples of (meth)acrylic compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin mono(meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate.
  • Hydroxy(meth)acrylate compounds such as 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri(meth)acrylate, and dipentaerythritol tri- or tetra(meth)acrylate; hydroxy(meth)acrylamide compounds such as N-hydroxyethyl(meth)acrylamide, and N,N-bis(2-hydroxyethyl)(meth)acrylamide.
  • the (meth)acrylic compound (E-2b) that does not have a urethane skeleton that can be obtained includes any combination of reaction products of the above-mentioned polyol having at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, and a (meth)acrylic compound having a hydroxyl group.
  • the weight average molecular weight (Mw) of the (meth)acrylic compound (E-2) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, and even more preferably from 3,000 to 20,000, from the viewpoint of the viscosity of the dental curable composition.
  • the weight average molecular weight (Mw) means a weight average molecular weight calculated in terms of polystyrene, determined by gel permeation chromatography (GPC).
  • the weight average molecular weight per (meth)acrylic group in the (meth)acrylic compound (E-2) is preferably 1,250 or more and less than 20,000, more preferably 1,500 or more and 17,500 or less, even more preferably 1,800 or more and 16,000 or less, and particularly preferably 2,500 or more and 15,000 or less.
  • the number of polymerizable groups in the (meth)acrylic compound (E-2a) is within the above range, appropriate crosslinking occurs, making it possible to maintain the mechanical strength of the cured product.
  • the (meth)acrylic compound (E-2) contains a polymerizable group other than the (meth)acrylic group, such as a vinyl group or a styrene group, the polymerization shrinkage stress may become large depending on the polymerization form. Therefore, the number of polymerizable groups other than the (meth)acrylic group in the (meth)acrylic compound (E-2) is preferably 2 or less, and more preferably 0.
  • the viscosity of the (meth)acrylic compound (E-2) at 25° C. is preferably from 1,000 to 10,000,000 mPa ⁇ s, more preferably from 5,000 to 7,500,000 mPa ⁇ s, and even more preferably from 10,000 to 7,000,000 mPa ⁇ s, from the viewpoint of the fluidity of the dental curable composition.
  • the viscosity of the (meth)acrylic compound (E-2) in the present invention means the viscosity measured by a Brookfield rotational viscometer at 25° C. Measurement conditions such as time and rotation speed are appropriately adjusted depending on the viscosity range.
  • (meth)acrylic compound (E-2) a commercially available product may be used.
  • commercially available products include urethane polymers having a polymerizable group at the end, such as the "Art Resin” series (UN-7600, UN-7700) manufactured by Negami Chemical Industrial Co., Ltd., and the "Kuraprene” series (LIR-30, LIR-50, LIR-390, LIR-403, LIR-410, UC-102M, UC-203M, LIR-70 ... LBR-302, LBR-307, LBR-305, LBR-352, LBR-361, L-SBR-820, L-SBR-841), polyols manufactured by Kuraray Co., Ltd.
  • liquid polybutadiene "NISSO-PB" (B-1000, B-2000, E-2000, BI-2000, BI-3000, G-1000, G-2000, G-3000, GI-1000, GI-2000, GI-3000, TEAI-1000, TE-2000, TE-4000, JP-100, JP-200) manufactured by Nippon Soda Co., Ltd., and the like.
  • the hydrophilic polymer (E-3) used in the present invention preferably has a hydrophilic group.
  • the hydrophilic group include functional groups such as a carboxyl group, an alkali metal salt of a carboxyl group, a sulfonic acid group, an alkali metal salt of a sulfonic acid group, a hydroxyl group, an amide group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group. These groups may be present at any position in the polymer.
  • the hydrophilic polymer (E-3) is adsorbed to the filler (B) via an adsorption group of the filler (B) (e.g., a silanol group that silica has on the particle surface) by the hydrophilic group, and the filler (B) and the hydrophilic polymer (E-3) form a crosslinked structure by hydrogen bonding, thereby obtaining the required specific viscosity behavior.
  • an adsorption group of the filler (B) e.g., a silanol group that silica has on the particle surface
  • hydrophilic polymers (E-3) examples include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid or polyacrylates, polymethacrylic acid, etc.
  • rheology modifier (E) other than the inorganic fine particles (E-1), the (meth)acrylic compound (E-2), and the hydrophilic polymer (E-3) known rheology modifiers can be used without limitation, such as cellulose nanofibers, cellulose derivatives, polymethacrylates, polysiloxanes and derivatives thereof (e.g., linear polysiloxane compounds, cyclic polysiloxane compounds, cage-type linear polysiloxane compounds), polyamide waxes, polyethylene oxide, organic acid dextrin compounds, dibenzylidene sorbitols, hydrogenated castor oil, ethylene-bis-hydroxystearic acid amide, and natural waxes such as carnauba wax. These may be used alone or in combination of two or more.
  • the dental hardenable compositions are free of polysiloxanes and their derivatives.
  • the content of the rheology control agent (E) other than the inorganic fine particles (E-1) may be the same as that of the inorganic fine particles (E-1).
  • the content of the rheology modifier (E) can be appropriately changed depending on the type of material so that the time T required for the viscosity V3 to reach 10,000 Pa ⁇ s after the shear rate is switched from D2 to D1 again is within the desired range.
  • the dental curable composition of the present invention may contain a polymerization inhibitor, an ultraviolet absorber, a solvent (e.g., water, an organic solvent), a pH adjuster, a colorant, an antibacterial agent, a fragrance, etc., within the scope of not impairing the effects of the present invention.
  • a polymerization inhibitor e.g., an ultraviolet absorber, a solvent (e.g., water, an organic solvent), a pH adjuster, a colorant, an antibacterial agent, a fragrance, etc.
  • the polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 2,6-di-t-butyl-4-methylphenol.
  • the content of a solvent (e.g., water, organic solvent) in the dental hardenable composition is preferably less than 1 mass %, more preferably less than 0.1 mass %, and even more preferably less than 0.01 mass %, based on the total amount (100 mass %) of the dental hardenable composition.
  • the dental hardenable composition of the present invention may be prepared according to a conventional method depending on the type and amount of the above-mentioned components.
  • the dental hardenable composition of the present invention is preferably used in a two-component form.
  • the two-component form may be appropriately selected from a powder and liquid form, a paste and liquid form, a two-paste form, and the like. In a more preferred embodiment from the viewpoint of ease of handling, it is used in the form of a two-paste type.
  • the paste is usually prepared by kneading the filler (B) (powder) with a liquid component prepared by mixing components other than the filler (B).
  • Certain preferred embodiments include dental hardenable compositions that are two-paste types, including a first part and a second part.
  • the first agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization initiator (C-2)
  • a dental hardenable composition in which the second agent contains a polymerizable monomer (A), a filler (B), and a chemical polymerization accelerator (D-2) is preferred.
  • a dental curable composition in which the first agent contains a hydroperoxide as the chemical polymerization initiator (C-2), and the second agent contains a polymerizable monomer (A), a filler (B), and a thiourea compound as the chemical polymerization accelerator (D-2) is preferred.
  • Another preferred embodiment is a dental hardenable composition of the two-paste type, in which at least one of the first agent and the second agent contains a transition metal compound of the fourth period.
  • the present invention includes various combinations of the above-mentioned configurations within the technical scope of the present invention, as long as the effects of the present invention are achieved.
  • HEMA 2-hydroxyethyl methacrylate #801: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane
  • Filler 1 The filler produced in the following Production Example 1-1 was used.
  • Filler 2 The filler produced in Production Example 1-2 below was used.
  • the average particle diameters of Filler 1 and Filler 2 were measured on a volume basis using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300") and a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.
  • SALD-2300 laser diffraction particle size distribution measuring device
  • each dental hardenable composition was prepared according to the formulations shown in Tables 1 to 3. Specifically, the following applies: When the rheology modifier (E) was a solid, the components other than the filler (B) and the rheology modifier (E) were mixed at room temperature to obtain a mixture, and then the mixture was mixed with the filler (B) and the rheology modifier (E) shown in Tables 1 to 3 to obtain a dental composition. When the rheology control agent (E) was liquid, the components other than the filler (B) were mixed to obtain a mixture, and then the mixture was mixed with the filler (B) shown in Tables 1 to 3 to obtain a dental composition.
  • the rheology control agent (E) was liquid, the components other than the filler (B) were mixed to obtain a mixture, and then the mixture was mixed with the filler (B) shown in Tables 1 to 3 to obtain a dental composition.
  • a rotational rheometer product name "AR2000", manufactured by TA Instruments Japan, Inc.
  • the average viscosity value from 30 s to 60 s after the start of the measurement was defined as viscosity V1
  • the average viscosity value from 90 s to 120 s after the start of the measurement was defined as viscosity V2.
  • Test Example 4 Removability of excess cement
  • the labial surface of a bovine mandibular anterior tooth was polished with silicon carbide paper under running water to expose a flat surface of the dentin.
  • the exposed flat surface was further polished with #1000 silicon carbide paper under running water, and then the water on the surface was dried by air blowing. After drying, 0.5 g of the dental curable composition of each Example and Comparative Example was applied to the smooth surface, and a 5 mm ⁇ 5 mm stainless steel plate was pressed against the composition.
  • Examples 3-1 to 3-11 Using a two-part dental hardenable composition consisting of a first part and a second part having the composition shown in Table 4, each property was evaluated in the same manner as described above.
  • a dental hardenable composition obtained by mixing equal amounts of the first and second agents shown in Table 4 for 10 seconds was used in place of the dental hardenable compositions of the examples and comparative examples in each of the above test examples.
  • the dental hardenable composition of the present invention is suitable for use as a dental cement in the field of dental care.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0357916B2 (https=) 1981-04-09 1991-09-03 Basf Ag
JP2001510146A (ja) * 1997-07-17 2001-07-31 ミネソタ マイニング アンド マニュファクチャリング カンパニー 取り扱い特性が改善された歯科用樹脂セメント
WO2008068862A1 (ja) * 2006-12-06 2008-06-12 Kabushiki Kaisha Shofu 歯科用樹脂系セメント組成物
JP2014111555A (ja) 2012-12-05 2014-06-19 Kuraray Noritake Dental Inc 歯科用硬化性組成物及びこれを用いた歯科用セメント
JP2019167334A (ja) 2018-03-20 2019-10-03 株式会社松風 除去性のよい歯科合着用グラスアイオノマーセメント組成物
WO2020111142A1 (ja) 2018-11-28 2020-06-04 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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0357916B2 (https=) 1981-04-09 1991-09-03 Basf Ag
JP2001510146A (ja) * 1997-07-17 2001-07-31 ミネソタ マイニング アンド マニュファクチャリング カンパニー 取り扱い特性が改善された歯科用樹脂セメント
WO2008068862A1 (ja) * 2006-12-06 2008-06-12 Kabushiki Kaisha Shofu 歯科用樹脂系セメント組成物
JP2014111555A (ja) 2012-12-05 2014-06-19 Kuraray Noritake Dental Inc 歯科用硬化性組成物及びこれを用いた歯科用セメント
JP2019167334A (ja) 2018-03-20 2019-10-03 株式会社松風 除去性のよい歯科合着用グラスアイオノマーセメント組成物
WO2020111142A1 (ja) 2018-11-28 2020-06-04 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

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