CN113677309A - Two-component curable dental composition - Google Patents
Two-component curable dental composition Download PDFInfo
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- CN113677309A CN113677309A CN202080021754.9A CN202080021754A CN113677309A CN 113677309 A CN113677309 A CN 113677309A CN 202080021754 A CN202080021754 A CN 202080021754A CN 113677309 A CN113677309 A CN 113677309A
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/836—Glass
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
One embodiment of the present invention relates to a two-component curable composition for dental use, which comprises a first agent comprising a (meth) acrylate and a diacyl peroxide, and a second agent comprising a (meth) acrylate and an aromatic tertiary amine, wherein the first agent and/or the second agent further comprises a compound represented by general formula (1) (wherein R is R1Is a hydrogen atom or a methyl group, R2Is a group capable of hydrolysis, R3Is a hydrocarbon group having 1 to 6 carbon atoms, p is 2 or 3, and q is an integer of 6 to 13. ) The surface-treated ionomer glass containing the silane coupling agentGlass particles.
Description
Technical Field
The present invention relates to a two-component curable composition for dental use.
Background
In the dental field, two-component composite resins are used in the formation of abutment teeth.
The two-component composite resin contains a (meth) acrylate, a filler, and a chemical polymerization initiator (an organic peroxide and a reducing agent), and further contains a photopolymerization initiator as needed.
Here, the two-component composite resin has a first agent containing an organic peroxide and a second agent containing a reducing agent. Furthermore, as the filler, fluorosilicate glass particles surface-treated with 3-methacryloxypropyltrimethoxysilane are used (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2008-247801.
Disclosure of Invention
Problems to be solved by the invention
However, it is desired to further improve the storage stability of the two-component composite resin and the flexural strength of the cured body.
An object of one embodiment of the present invention is to provide a two-component curable composition for dental use, which can improve storage stability and flexural strength of a cured product.
Means for solving the problems
The present invention provides a two-component curable dental composition comprising a first agent comprising a (meth) acrylate and a diacylperoxide and a second agent comprising a (meth) acrylate and an aromatic tertiary amine, wherein the first agent and/or the second agent further comprises ionomer glass particles surface-treated with a silane coupling agent represented by general formula (1),
[ solution 1]
(in the formula, R1Is a hydrogen atom or a methyl group, R2Is a group capable of hydrolysis, R3Is a hydrocarbon group having 1 to 6 carbon atoms, p is 2 or 3, and q is an integer of 6 to 13. ).
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, a two-component curable composition for dental use can be provided which can improve storage stability and flexural strength of a cured product.
Detailed Description
The present embodiment will be described below. The present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the invention as set forth in the claims.
[ two-component curable dental composition ]
The two-component curable composition for dental use of the present embodiment has a first agent containing a (meth) acrylate and a diacylperoxide and a second agent containing a (meth) acrylate and an aromatic tertiary amine, and therefore the flexural strength of the cured product is improved. Further, the first agent and/or the second agent further contain ionomer glass particles surface-treated with a silane coupling agent represented by the general formula (1),
[ solution 2]
(in the formula, R1Is a hydrogen atom or a methyl group, R2Is a group capable of hydrolysis, R3Is a hydrocarbon group having 1 to 6 carbon atoms, p is 2 or 3, and q is an integer of 6 to 13. )
Therefore, the two-component curable dental composition of the present embodiment has improved storage stability.
[ (non-surface treated) ionomer glass particles ]
The difference in pH of the ionomer glass particles calculated by the formula S (pH) -R (pH) is preferably 0.2 or more, more preferably 0.35 or more,
(wherein R (pH) is the pH of an acidic solution prepared by mixing distilled water and ethanol at a volume ratio of 1:1 and then dissolving phosphoric acid to adjust the pH at 23 ℃ to 2.50. + -. 0.03, and S (pH) is the pH at 23 ℃ of a dispersion of 1.0g of ionomer glass particles dispersed in 20g of the acidic solution.)
When the difference in pH between the ionomer glass particles is 0.2 or more, the storage stability of the two-component curable dental composition of the present embodiment is further improved.
Examples of the ionomer glass include fluorosilicate glass; a glass containing zinc, silicon, and fluorine (hereinafter referred to as zinc-fluorine glass) (see, for example, international publication No. 2006/050829 and international publication No. 2017/168336), and the like.
Two or more species of the ionomer glass particles may be used in combination.
(Fluoroaluminosilicate glass)
The content of silicon in the fluorosilicate glass is converted to silicon oxide (SiO)2) The amount of (B) is preferably 20 to 50% by mass, and more preferably 20 to 35% by mass.
The content of aluminum in the fluorosilicate glass is converted to alumina (Al)2O3) The amount of (b) is preferably 20 to 40% by mass, and more preferably 20 to 30% by mass.
The content of phosphorus in the fluorosilicate glass is converted to phosphorus (V) (P) oxide2O5) The amount of (b) is preferably 0 to 15% by mass, more preferably 3 to 10% by mass.
The content of strontium in the fluorosilicate glass is preferably 15 to 40 mass%, and more preferably 15 to 30 mass%, in terms of strontium oxide (SrO).
In fluorosilicate glassesSodium content in terms of sodium oxide (Na)2O) is preferably 0 to 15% by mass, more preferably 1 to 10% by mass.
The fluorine (F) content in the fluorosilicate glass is preferably 1 to 30 mass%, and more preferably 3 to 20 mass%.
(Zinc fluorine glass)
The zinc content in the zinc-fluorine glass is preferably 10 to 60 mass%, more preferably 20 to 55 mass%, in terms of zinc oxide (ZnO).
The content of silicon in the zinc-fluorine glass is converted into silicon oxide (SiO)2) The amount of (b) is preferably 15 to 50% by mass, and more preferably 20 to 40% by mass.
The content of fluorine (F) in the zinc-fluorine glass is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass.
The content of calcium in the zinc fluorine glass is preferably 0 to 30% by mass, and more preferably 5 to 20% by mass, in terms of calcium oxide (CaO).
The content of phosphorus in the zinc-fluorine glass is converted into phosphorus (V) (P) oxide2O5) The amount of (b) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass.
The strontium content in the zinc-fluorine glass is preferably 0 to 40% by mass, more preferably 10 to 30% by mass, in terms of strontium oxide (SrO).
The lanthanum content in the zinc-fluorine glass is converted into lanthanum oxide (La)2O3) The amount of (b) is preferably 0 to 50% by mass, and more preferably 10 to 40% by mass.
The content of sodium in the zinc fluoride glass is converted into sodium oxide (Na)2O) is preferably 0 to 15% by mass, more preferably 1 to 10% by mass.
The content of potassium in the zinc fluoride glass is converted into potassium oxide (K)2O) is preferably 0 to 10% by mass, more preferably 1 to 5% by mass.
The content of aluminum in the zinc fluoride glass is converted into aluminum oxide (Al)2O3) Preferably 0 to 35% by mass, and more preferably 0 to up to0.5% by mass.
[ silane coupling agent represented by the general formula (1) ]
As R in the general formula (1)2The hydroxyl group is not particularly limited as long as it can be hydrolyzed to form a hydroxyl group, and examples thereof include alkoxy groups such as methoxy group, ethoxy group, and butoxy group, chlorine atom, and isocyanate group.
As R in the general formula (1)3Examples of the alkyl group include, but are not particularly limited to, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms.
The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The alkenyl group having 2 to 6 carbon atoms may be any of straight-chain, branched-chain and cyclic, and examples thereof include vinyl, allyl, methylvinyl, butenyl, pentenyl, hexenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.
The alkynyl group having 2 to 6 carbon atoms may be any of straight, branched and cyclic, and examples thereof include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl-3-butynyl, and the like.
Q in the general formula (1) is an integer of 6 to 13, preferably an integer of 8 to 13.
Examples of the silane coupling agent represented by the general formula (1) include 6-methacryloyloxyhexyltrimethoxysilane, 7-methacryloyloxyheptyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, 8-methacryloyloxyoctyltriethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 11-methacryloyloxyundecyldichloromethylsilane, 11-methacryloyloxyundecyltrichlorosilane, 11-methacryloyloxyundecyldimethoxymethylsilane, 12-methacryloyloxydodecyltrimethoxysilane, and the like, 13-methacryloxytridecyltrimethoxysilane, and the like. Among these, 8-methacryloyloxyoctyltrimethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane and 11-methacryloyloxyundecyltrimethoxysilane are preferable.
Two or more silane coupling agents represented by the general formula (1) may be used in combination.
[ method for treating surface of ionomer glass particles ]
Examples of the method of surface-treating the ionomer glass particles include a method of spraying a solution of a silane coupling agent represented by the general formula (1) diluted with a solvent while stirring the ionomer glass particles in a mixing tank, and heating and drying the solution; a method comprising stirring and mixing ionomer glass particles and a silane coupling agent represented by general formula (1) in a solvent, and then heating and drying the mixture.
The mass ratio of the silane coupling agent represented by the general formula (1) to the ionomer glass particles is preferably 0.005 to 0.15, and more preferably 0.01 to 0.13.
[ ionomer glass particles having surface treated ]
The volume median particle diameter of the surface-treated ionomer glass particles is preferably 0.1 to 1.5 μm, and more preferably 0.3 to 1.2. mu.m. The bending strength of the cured product of the two-component curable dental composition of the present embodiment is further improved when the volume median particle diameter of the surface-treated ionomer glass particles is 0.1 μm or more, and the cutting feeling of the cured product of the two-component curable dental composition of the present embodiment is improved when the volume median particle diameter is 1.5 μm or less.
The content of the surface-treated ionomer glass particles in the curable two-pack dental composition of the present embodiment is preferably 20 to 90% by mass, and more preferably 40 to 85% by mass. The bending strength of the cured product of the two-component curable dental composition of the present embodiment is further improved if the content of the surface-treated ionomer glass particles in the two-component curable dental composition of the present embodiment is 20% by mass or more, and the workability of the two-component curable dental composition of the present embodiment is improved if the content is 90% by mass or less.
[ (meth) acrylic acid ester ]
In the present specification and claims, the term (meth) acrylate refers to a compound (for example, a monomer, an oligomer, a prepolymer, or the like) having 1 or more methacryloxy groups and/or acryloxy groups (hereinafter referred to as (meth) acryloxy groups).
Two or more kinds of (meth) acrylates may be used in combination.
The content of the (meth) acrylate in the two-component curable dental composition of the present embodiment is preferably 10 to 60% by mass, and more preferably 15 to 50% by mass. The handling property of the two-component curable dental composition of the present embodiment is further improved if the (meth) acrylate content in the two-component curable dental composition of the present embodiment is 10% by mass or more, and the flexural strength of the cured product of the two-component curable dental composition of the present embodiment is further improved if the (meth) acrylate content is 60% by mass or less.
The (meth) acrylate preferably has no acid group.
Examples of the (meth) acrylic ester having no acid group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethoxy (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethyl (meth) acrylate, 2-acryloyloxypropane, 3-acrylate, 3-2-, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polybutylene glycol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, di-2- (meth) acryloyloxyethyl-2, 4-trimethylhexamethylene dicarbamate, 1,3, 5-tris [1, 3-bis { (meth) acryloyloxy } -2-propoxycarbonylaminohexane ] -1,3,5- (1H,3H,5H) triazine-2, 4, 6-trione, 2-bis [4- (3- (meth) acryloyloxy-2-hydroxypropyl) ] phenylpropane, N '- (2,2, 4-trimethylhexamethylene) bis [ 2- (aminocarboxy) propane-1, 3-diol ] tetramethacrylate, a (meth) acrylate of a urethane oligomer comprising 2, 2' -bis (4-hydroxycyclohexyl) propane, 2-caprolactone, 1, 6-hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, a process for preparing a compound by reacting a compound of formula (I) with a compound of formula (I), (meth) acrylate of urethane oligomer containing 1, 3-butanediol, 1, 6-hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate, and the like.
The (meth) acrylate having no acid group preferably has 2 or more (meth) acryloyloxy groups. As a result, the cured product of the two-component curable dental composition of the present embodiment has further improved flexural strength.
[ diacyl peroxide ]
Examples of the diacyl peroxide include benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide and the like.
Two or more kinds of diacyl peroxides may be used in combination.
The content of the diacyl peroxide in the two-component curable dental composition of the present embodiment is preferably 0.05 to 1.5% by mass, and more preferably 0.2 to 1.2% by mass. The bending strength of the cured product of the two-component curable dental composition of the present embodiment is further improved if the content of the diacyl peroxide in the two-component curable dental composition of the present embodiment is 0.1% by mass or more, and the storage stability of the two-component curable dental composition of the present embodiment is further improved if the content is 1.5% by mass or less.
[ aromatic Tertiary amines ]
Examples of the aromatic tertiary amine include N, N-dimethyl-p-toluidine, N-dimethylaniline, N-methyl-N- β -hydroxyaniline, N-bis (. beta. -hydroxyethyl) -aniline, N-bis (. beta. -hydroxyethyl) -p-toluidine, N-bis (. beta. -hydroxypropyl) -aniline, N-bis (. beta. -hydroxypropyl) -p-toluidine, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, and the like.
Two or more kinds of the aromatic tertiary amines may be used in combination.
The content of the aromatic tertiary amine in the two-component curable composition for dental use of the present embodiment is preferably 0.05 to 1.5% by mass, and more preferably 0.2 to 1.2% by mass. The flexural strength of the cured product of the two-component curable dental composition of the present embodiment is further improved if the content of the aromatic tertiary amine in the two-component curable dental composition of the present embodiment is 0.05% by mass or more, and the storage stability of the two-component curable dental composition of the present embodiment is further improved if the content is 1.5% by mass or less.
[ photopolymerization initiator ]
The two-component curable dental composition of the present embodiment may further contain a photopolymerization initiator.
In addition, when the two-component curable composition for dental use of the present embodiment includes a photopolymerization initiator, the two-component curable composition for dental use of the present embodiment may further include a photopolymerization accelerator.
[ Filler ]
The two-component curable dental composition of the present embodiment may further contain a filler (hereinafter, referred to as a filler) other than the surface-treated ionomer glass particles. In this way, the viscosity of the two-component curable dental composition of the present embodiment can be adjusted.
The filler may be either one of an organic filler and an inorganic filler, and is preferably an inorganic filler.
Examples of the inorganic filler include silica particles, alumina particles, and glass particles (e.g., barium glass particles and strontium glass particles).
The inorganic filler may be surface-treated with a surface-treating agent such as a silane coupling agent, if necessary.
Two or more kinds of fillers may be used in combination.
The content of the filler in the two-component curable dental composition of the present embodiment is preferably 0.05 to 10% by mass, and more preferably 0.1 to 3% by mass.
[ other ingredients ]
The two-component curable composition for dental use of the present embodiment may further contain a polymerization inhibitor and the like.
Examples of the polymerization inhibitor include dibutylhydroxytoluene and 2, 6-tert-butyl-2, 4-xylenol.
Two or more kinds of polymerization inhibitors may be used in combination.
The content of the polymerization inhibitor in the two-component curable dental composition of the present embodiment is preferably 0 to 0.5% by mass, and more preferably 0 to 0.2% by mass.
[ method of Using two-pack curable composition for dental applications ]
The two-component curable dental composition can be provided, for example, as a dental composition having: a syringe filled with the first dose and the second dose, a plunger into which the syringe is fitted from the rear end side of the syringe, and a needle tip attached to the tip of the syringe. For example, the set includes 2 syringes connected in parallel and 2 plungers connected in parallel, and the syringes each include a static mixer at the tip thereof.
Here, the needle tip has a needle inner diameter of usually 0.3 to 0.9 mm.
[ use of two-component curable composition for dental applications ]
The two-component curable composition for dental use of the present embodiment can be suitably used for, for example, a composite resin for abutment tooth formation, a resin cement, a composite resin for filling, and the like.
Examples
Hereinafter, examples of the present invention will be described, but the present invention is not limited to the examples.
Examples 1 to 11 and comparative examples 1 and 2
Paste a and paste B (two-component composite resin) were prepared by mixing (meth) acrylate, an oxidizing agent or reducing agent in a chemical polymerization initiator, a polymerization inhibitor, and a filler in the amounts shown in table 1 (mass%).
The meanings of abbreviations and the preparation methods in table 1 are as follows.
UDMA: bis-2-methacryloyloxyethyl-2, 2, 4-trimethylhexamethylene dicarbamate.
GDMA: 2-hydroxy-1, 3-dimethacryloxypropane.
TEGDMA: triethylene glycol dimethacrylate.
bis-MEPP: 2, 2-bis [4- (methacryloyloxyethoxy) phenyl ] propane.
DEPT: n, N-dihydroxyethyl-p-toluidine.
BPO: benzoyl peroxide.
CHP: cumene hydroperoxide.
BDMF: 2-tert-butyl-4, 6-dimethylphenol.
BHT: dibutylhydroxytoluene.
Silica particles: hydrophilic fumed silica OX50 (manufactured by Japan Aerosil).
(MOTS treatment method for producing ionomer glass particles A)
Silicic anhydride (SiO)2) Aluminum fluoride (AlF)3) Phosphorus oxide (P)2O5) Strontium fluoride (SrF)2) Sodium fluoride (NaF) was mixed at a predetermined ratio, and then sufficiently mixed in a mortar to obtain a raw material composition. Next, the raw material composition was placed in a magnetic crucible, and then allowed to stand in an electric furnace. Next, the electric furnace was heated to 1200 to 1400 ℃, and the raw material composition was melted and homogenized, and then cooled in the air, to obtain fluorosilicate glass. Next, after the fluorosilicate glass was pulverized for 20 hours using a ball mill, it was passed through a 120-mesh sieve to obtain fluorosilicate glass particles, i.e., ionomer glass particles a. The difference in pH of the ionomer glass particles A was 0.38. Further, the composition of the ionomer glass particles A was analyzed by using a fluorescent X-ray analyzer ZSX Primus II (manufactured by Rigaku corporation), and as a result, it was SiO2(31.1% by mass), Al2O3(26.1% by mass), Na2O (6.5 mass%), P2O5(3.3 mass%), SrO (19.2 mass%), F (13.8 mass%).
Ionomer glass particles a (100 parts by mass) and 8-Methacryloxyoctyltrimethoxysilane (MOTS) (2 parts by mass) were mixed and then heated and dried to obtain ionomer glass particles a surface-treated with MOTS, that is, MOTS-treated ionomer glass particles a. The volume median particle diameter of MOTS-treated ionomer glass particles A was 0.8. mu.m.
(MOTS treatment method for producing ionomer glass particles B)
Mixing zinc oxide (ZnO), silicic anhydride (SiO)2) Calcium fluoride (CaF)2) Calcium phosphate (Ca)3(PO4)2) Strontium fluoride (SrF)2) Phosphorus oxide (P)2O5) Lanthanum oxide (La)2O3) Sodium fluoride (NaF) and potassium bicarbonate (KHCO)3) After mixing at a predetermined ratio, the mixture was stirred in a mortar,thoroughly mixed to obtain a raw material composition. Next, the raw material composition was placed in a platinum crucible, and then placed in an electric furnace. Next, the electric furnace was heated up to 1300 ℃, and the raw material composition was melted and homogenized, and then flowed out into water, thereby obtaining bulk zinc fluoride glass. Next, the zinc fluorine glass in a bulk form was pulverized for 20 hours using an alumina ball mill, and then passed through a 120-mesh sieve, thereby obtaining zinc fluorine glass particles, i.e., ionomer glass particles B. The difference in pH of ionomer glass particles B was 0.57. Further, the composition of the ionomer glass particles B was analyzed using a fluorescent X-ray analyzer ZSX Primus II (manufactured by Rigaku), and as a result, ZnO (25.2 mass%) and SiO2(26.8 mass%), F (5.8 mass%), CaO (6.6 mass%), La2O3(33.2% by mass), K2O (2.2 mass%), Al2O3(0.2 mass%).
Ionomer glass particles B surface-treated with MOTS, that is, MOTS-treated ionomer glass particles B were obtained in the same manner as MOTS-treated ionomer glass particles a except that ionomer glass particles B were used instead of ionomer glass particles a. The volume median particle diameter of the MOTS-treated ionomer glass particles B was 0.8. mu.m.
(MPTS treatment of ionomer glass particles A preparation)
Fluorosilicate glass particles surface-treated with MPTS, i.e., MPTS-treated ionomer glass particles a, were obtained in the same manner as MOTS-treated ionomer glass particles a except that 3-Methacryloxypropyltrimethoxysilane (MPTS) was used instead of MOTS. MPTS treated ionomer glass particle A had a volume median particle size of 0.8 μm.
(MOTS barium glass particle production)
Barium glass particles surface-treated with MOTS, that is, MOTS-treated barium glass particles were obtained in the same manner as MOTS-treated ionomer glass particles A except that barium glass particles G018-053 Ultra Fine 0.7 (Shot) were used instead of ionomer glass particles A. The difference in pH of the barium glass particles was 0.09. Further, the volume median particle diameter of the MOTS-treated barium glass particles was 0.7. mu.m.
(method of measuring volume median diameter of glass particles)
After 15mg of glass particles were added to 20mL of a 0.2 mass% aqueous solution of sodium hexametaphosphate, the mixture was dispersed for 30 minutes using an ultrasonic disperser, and a glass particle dispersion was obtained. Next, the volume median diameter of the glass particles was measured using a laser diffraction/scattering particle diameter distribution measuring apparatus LA-950 (manufactured by HORIBA).
[ difference in pH ]
After distilled water and ethanol were mixed at a volume ratio of 1:1 in a glass bottle having an inner diameter of 40mm and a height of 75mm, phosphoric acid was dissolved to adjust the pH at 23 ℃ to 2.50. + -. 0.03(R (pH)) to obtain an acidic solution.
1.0g of glass particles which were not surface-treated were added to 20g of the acidic solution, and after stirring at 300rpm for 2 minutes using a stirrer having a diameter of 7mm and a length of 20mm, the pH (S (pH)) at 23 ℃ was measured immediately. Next, the difference in pH was calculated by the formula S (pH) -R (pH).
Next, the storage stability of the two-component composite resin, the flexural strength of the cured product, and the cut feeling of the cured product were evaluated.
[ storage stability of two-component composite resin ]
The curing time of the two-component composite resin was measured before and after 12 months of storage at 23 ℃ in the following manner, and the storage stability of the two-component composite resin was evaluated. The two-component composite resin was stored at 23 ℃ for 12 months, and the change in curing time of the two-component composite resin was within ± 100 seconds.
[ curing time of two-component composite resin ]
After collecting the paste A and the paste B at a mass ratio of 1:1, kneading was performed for 10 seconds. Subsequently, kneaded materials of paste a and paste B were filled into a cylindrical mold having a diameter of 4mm and a height of 4mm, and then a temperature change accompanying curing of the kneaded materials of paste a and paste B was measured using a radiation thermometer. Here, the curing time is a time from the start of kneading of the paste a and the paste B until the temperature of the kneaded material of the paste a and the paste B becomes the highest. In addition, if the curing time of the two-component composite resin is 180 seconds or more, there is no clinical problem.
[ flexural Strength of cured product of two-component composite resin ]
After collecting the paste A and the paste B at a mass ratio of 1:1, kneading was performed for 10 seconds. Next, the kneaded materials of paste A and paste B were filled into a 2 mm. times.2 mm. times.25 mm prism mold, and then stored at 37 ℃ for 1 hour to cure the kneaded materials of paste A and paste B. Next, the cured product of kneaded materials of paste a and paste B was removed from the prism mold, and then burrs were removed to obtain a cured product of a two-component composite resin. Next, the cured product of the two-component composite resin was immersed in water at 37 ℃ for 23 hours, and then the flexural strength of the cured product of the two-component composite resin was measured using an autograph at a crosshead speed of 1.0 mm/min. In addition, the bending strength of the cured product of the two-component composite resin was determined to be 140MPa or more.
[ cutting feeling of cured product of two-component composite resin ]
After collecting the paste A and the paste B at a mass ratio of 1:1, kneading was performed for 10 seconds. Next, the kneaded materials of paste A and paste B were filled into a cylindrical mold having a diameter of 6.5mm and a height of 20mm, and then stored at 37 ℃ for 1 hour to cure the kneaded materials of paste A and paste B. Next, using CERASMART PREPARATION BUR SET BR2 (manufactured by GC), the cured product of the two-component composite resin was cut, and the cut feeling of the cured product of the two-component composite resin was evaluated. In addition, it was determined that the cured product of the two-component composite resin had a cutting feel equal to or greater than that of bovine ivory dentin.
Table 1 shows the results of evaluation of the storage stability of the two-component composite resin, the flexural strength of the cured product, and the cut feeling of the cured product.
As is clear from Table 1, the two-component composite resins of examples 1 to 11 were high in storage stability and flexural strength of the cured product.
In contrast, the two-component composite resin of comparative example 1 had low storage stability because it contained barium glass particles surface-treated with 8-methacryloxyoctyltrimethoxysilane (MOTS-treated barium glass particles).
Further, the two-component composite resin of comparative example 2 contains fluorosilicate glass particles surface-treated with 3-methacryloxypropyltrimethoxysilane (MPTS-treated ionomer glass particles), and thus storage stability and flexural strength of the cured body are low.
This application claims priority to basic application No. 2019-.
Claims (7)
1. A two-component curable dental composition comprising:
a first agent comprising a (meth) acrylate and a diacyl peroxide; and
a second agent comprising a (meth) acrylate and an aromatic tertiary amine,
the first agent and/or the second agent further contain ionomer glass particles surface-treated with a silane coupling agent represented by general formula (1),
[ solution 1]
In the formula, R1Is a hydrogen atom or a methyl group, R2Is a group capable of hydrolysis, R3Is a hydrocarbon group having 1 to 6 carbon atoms, p is 2 or 3, and q is an integer of 6 to 13.
2. The two-component curable dental composition according to claim 1,
the difference in pH, calculated from the formula S (pH) -R (pH), of the ionomer glass particles not subjected to the surface treatment is 0.2 or more,
wherein R (pH) is the pH of an acidic solution prepared by mixing distilled water and ethanol at a volume ratio of 1:1 and then dissolving phosphoric acid to adjust the pH at 23 ℃ to 2.50. + -. 0.03, and S (pH) is the pH at 23 ℃ of a dispersion of 1.0g of the ionomer glass particles which have not been subjected to the surface treatment and dispersed in 20g of the acidic solution.
3. The curable two-pack dental composition according to claim 1, wherein the volume median particle diameter of the surface-treated ionomer glass particles is 0.1 μm or more and 1.5 μm or less.
4. The curable two-pack dental composition according to claim 1, wherein the surface-treated ionomer glass particles are contained in an amount of 20 to 90 mass%.
5. The two-part curable dental composition according to claim 1, wherein the content of the diacyl peroxide is 0.1% by mass or more and 1.5% by mass or less.
6. The two-part curable dental composition according to claim 1, wherein the aromatic tertiary amine is contained in an amount of 0.1 to 1.5% by mass.
7. The two-part curable dental composition according to claim 1, which is used for the formation of abutment teeth.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-061732 | 2019-03-27 | ||
| JP2019061732 | 2019-03-27 | ||
| PCT/JP2020/001022 WO2020195028A1 (en) | 2019-03-27 | 2020-01-15 | Two-pack dental curable composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113677309A true CN113677309A (en) | 2021-11-19 |
Family
ID=72611318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080021754.9A Pending CN113677309A (en) | 2019-03-27 | 2020-01-15 | Two-component curable dental composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7220278B2 (en) |
| KR (1) | KR20210126700A (en) |
| CN (1) | CN113677309A (en) |
| WO (1) | WO2020195028A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100152318A1 (en) * | 2004-11-12 | 2010-06-17 | Gordon Blackwell | Dental glass composition |
| JP2011225526A (en) * | 2010-03-30 | 2011-11-10 | Kuraray Medical Inc | Portion pack type polymerizable support base construction material for dental use |
| JP2016008211A (en) * | 2014-06-26 | 2016-01-18 | クラレノリタケデンタル株式会社 | Dental restorative material composition |
| JP2016124811A (en) * | 2014-12-26 | 2016-07-11 | クラレノリタケデンタル株式会社 | Two paste-type dental hardening composition |
| WO2018070544A1 (en) * | 2016-10-15 | 2018-04-19 | Ｙａｍａｋｉｎ株式会社 | Dental composition and dental-cutting processing composite resin material using said dental composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4717167B2 (en) * | 1998-11-02 | 2011-07-06 | 株式会社クラレ | Adhesive composition for metal materials |
| JP5154126B2 (en) * | 2007-03-30 | 2013-02-27 | 株式会社ジーシー | Composite resin for abutment tooth construction |
| JP5325633B2 (en) * | 2009-03-30 | 2013-10-23 | クラレノリタケデンタル株式会社 | Two-part dental adhesive |
| JP6279391B2 (en) * | 2014-03-31 | 2018-02-14 | 株式会社松風 | High-tough dentin adhesive silane coupling agent and dental composition containing the same |
| KR20170117553A (en) * | 2015-03-20 | 2017-10-23 | 가부시키가이샤 지씨 | DENTAL CURABLE COMPOSITION AND METHOD FOR PRODUCING THE SAME |
| CN111050731B (en) * | 2017-08-28 | 2023-06-20 | 可乐丽则武齿科株式会社 | Non-solvent dental adhesive composition |
-
2020
- 2020-01-15 KR KR1020217029451A patent/KR20210126700A/en not_active Application Discontinuation
- 2020-01-15 JP JP2021508111A patent/JP7220278B2/en active Active
- 2020-01-15 CN CN202080021754.9A patent/CN113677309A/en active Pending
- 2020-01-15 WO PCT/JP2020/001022 patent/WO2020195028A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100152318A1 (en) * | 2004-11-12 | 2010-06-17 | Gordon Blackwell | Dental glass composition |
| JP2011225526A (en) * | 2010-03-30 | 2011-11-10 | Kuraray Medical Inc | Portion pack type polymerizable support base construction material for dental use |
| JP2016008211A (en) * | 2014-06-26 | 2016-01-18 | クラレノリタケデンタル株式会社 | Dental restorative material composition |
| JP2016124811A (en) * | 2014-12-26 | 2016-07-11 | クラレノリタケデンタル株式会社 | Two paste-type dental hardening composition |
| WO2018070544A1 (en) * | 2016-10-15 | 2018-04-19 | Ｙａｍａｋｉｎ株式会社 | Dental composition and dental-cutting processing composite resin material using said dental composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210126700A (en) | 2021-10-20 |
| WO2020195028A1 (en) | 2020-10-01 |
| JP7220278B2 (en) | 2023-02-09 |
| JPWO2020195028A1 (en) | 2020-10-01 |
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