WO2012086189A1 - 歯科用硬化性組成物 - Google Patents
歯科用硬化性組成物 Download PDFInfo
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- WO2012086189A1 WO2012086189A1 PCT/JP2011/007125 JP2011007125W WO2012086189A1 WO 2012086189 A1 WO2012086189 A1 WO 2012086189A1 JP 2011007125 W JP2011007125 W JP 2011007125W WO 2012086189 A1 WO2012086189 A1 WO 2012086189A1
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- 0 *c1c(*)c(*)c(*)c2c1*(I)I=*2 Chemical compound *c1c(*)c(*)c(*)c2c1*(I)I=*2 0.000 description 2
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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
- A61K6/884—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
Definitions
- the present invention relates to a dental curable composition containing an acidic group-containing polymerizable monomer. More specifically, the present invention relates to a dental curable composition having excellent curability and small discoloration of a cured product due to hydrogen sulfide in the oral cavity environment.
- Dental curable compositions used as dental cements, dental adhesives, composite resins, self-adhesive composite resins, sealants, dental room temperature polymerization resins, etc. contain a polymerizable monomer and a radical polymerization initiator. Curable compositions are widely used.
- Radical polymerization initiators are broadly classified into photopolymerization initiators and chemical polymerization initiators. In recent years, dual-cure products containing both are widely used in clinical practice.
- the chemical polymerization initiator is generally a combination of an oxidizing agent and a reducing agent. By mixing these, a so-called redox reaction occurs, a radical is generated, and the polymerization reaction is performed. Starting and curing proceeds.
- a dental composition containing a redox polymerization initiator is usually stored divided into a composition containing an oxidizing agent and a composition containing a reducing agent, and both compositions are mixed and used immediately before use.
- dental curable compositions are generally acidic.
- a radical polymerization initiator containing a copper compound has been proposed as a redox polymerization initiator used in a composition containing such an acidic component.
- Patent Document 1 proposes a redox initiator containing barbituric acid or thiobarbituric acid, peroxodisulfate and / or peroxodiphosphate compound, sulfinic acid compound, and copper compound.
- Patent Document 2 proposes a two-component initiator system having a hydroperoxide having a specific structure, a thiourea derivative, and a copper compound as an accelerator.
- copper compounds are known to turn black due to hydrogen sulfide produced by caries bacteria in the oral cavity environment, and when used in dental compositions, it is desirable to keep them in trace amounts.
- An object of the present invention is to provide a dental curable composition having excellent curability and small discoloration of a cured product due to hydrogen sulfide in the oral cavity environment.
- the present inventors have added a benzotriazole compound represented by the following general formula (1) to a composition containing a copper compound and an acidic group-containing polymerizable monomer, and
- a benzotriazole compound represented by the following general formula (2) is blended, the catalytic activity of the copper compound is remarkably improved, the reaction of the copper compound with hydrogen sulfide is suppressed, the curability is excellent, and the oral environment
- the present inventors have found that a composition having a small discoloration of a cured product due to hydrogen sulfide can be obtained, and the present invention has been completed.
- the present invention includes an acidic group-containing polymerizable monomer (a) as a polymerizable monomer component; a copper compound (b) as a polymerization initiator system component, and a benzoate represented by the following general formula (1).
- a dental curable composition comprising a triazole compound and / or a benzimidazole compound (c) represented by the following general formula (2).
- R 1 to R 8 each independently represents 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 present invention also provides an acidic group-containing polymerizable monomer (a) as a polymerizable monomer component and a benzotriazole represented by the above general formula (1) as a polymerization initiator system component. It is a dental curable composition containing a compound and / or a copper salt of the benzimidazole compound (c) represented by the general formula (2).
- the dental curable composition of the present invention is excellent in curability and has little discoloration of the cured product due to hydrogen sulfide in the oral cavity environment.
- the dental curable composition of the present invention contains an acidic group-containing polymerizable monomer (a) as a polymerizable monomer component, and a copper compound (b) and benzotriazole as polymerization initiator components.
- the acidic group-containing polymerizable monomer (a) has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and acryloyl. And a polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, a vinyl group, and a styrene group.
- the acidic group-containing polymerizable monomer (a) has an affinity for the adherend and has a decalcifying action on the tooth.
- the acidic group-containing polymerizable monomer (a) preferably has an acryloyl group or a methacryloyl group as the polymerizable group from the viewpoint of polymerizability, and more preferably has a methacryloyl group from the viewpoint of safety to the living body. preferable. Specific examples of the acidic group-containing polymerizable monomer (a) will be described below. In the following description, (meth) acrylic is a generic term for methacrylic and acrylic.
- Phosphoric acid group-containing polymerizable monomers 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) acryloyloxyoctyl dihydrophosphate Genphosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyl Oxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide dec
- Examples of the pyrophosphate group-containing polymerizable monomer include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meth) acryloyl pyrophosphate.
- Examples thereof include oxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and ammonium salts thereof.
- Examples of the thiophosphate group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- (meth) acryloyloxybutyldihydro Genthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- (meta ) Acryloyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydrogen Phosphate, 11- (meth) acryloyloxyundecyl dihydrogen thio
- Examples of the phosphonic acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxyhexyl-3.
- -Phosphonopropionate 10- (meth) acryloyloxydecyl-3-phosphonopropionate
- Illustrative are phosphonoacetates and their acid chlorides, alkali metal salts and ammonium salts.
- Examples of the sulfonic acid group-containing polymerizable monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth) acrylate.
- Examples of the carboxylic acid group-containing polymerizable monomer include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.
- Examples of the polymerizable monomer having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 2-
- Examples of the polymerizable monomer having a plurality of carboxyl 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) acryloyloxidedecane-1,1-dicarboxylic acid, 13- ( (Meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxybutyl trimellitate Tate, 4- (meth) acrylo
- the above acidic group-containing polymerizable monomer may be used alone or in combination of two or more.
- these acidic group-containing polymerizable monomers 10- (meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrochloride are used because of their high adhesion strength to the adherend.
- Genphosphate 2- (meth) acryloyloxyethyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxyethyl trimellitate, 2- (meth) acrylamide-2 -Methylpropanesulfonic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid is preferred.
- the blending amount of the acidic group-containing polymerizable monomer (a) is preferably 1 to 50 parts by weight in 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition of the present invention.
- the amount is more preferably 2 to 40 parts by weight, and further preferably 5 to 30 parts by weight.
- the blending amount of the acidic group-containing polymerizable monomer is 1 part by weight or more, it is easy to obtain high adhesion to various adherends, and the blending amount of the acidic group-containing polymerizable monomer is If it is 50 parts by weight or less, it is easy to maintain a balance between polymerizability and adhesiveness.
- the total amount of the polymerizable monomer component refers to the total amount of the acidic group-containing polymerizable monomer (a) and the polymerizable monomer (f) having no acidic group described later.
- the copper compound (b) is preferably a compound soluble in the polymerizable monomer component.
- Specific examples thereof include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, methacrylate Acid copper, 4-cyclohexyl butyrate copper; ⁇ -diketone copper: acetylacetone copper, trifluoroacetylacetone copper, hexafluoroacetylacetone copper, 2,2,6,6-tetramethyl-3,5-heptanedionate copper, benzoylacetone copper; ⁇ -ketoester copper as copper acetoacetate; copper alkoxide as copper methoxide, copper ethoxide, copper isopropoxide, copper 2- (2-butoxyethoxy) ethoxide, copper 2- (2-methoxyethoxy) ethoxide;
- carboxylate copper, ⁇ -diketone copper, and ⁇ -ketoester copper are preferable, and copper acetate and acetylacetone copper are particularly preferable.
- the content of the copper compound (b) can be made smaller than before.
- the content of the copper compound (b) is from 0 to 100 parts by weight with respect to the total amount of the polymerizable monomer components in the dental curable composition from the viewpoints of adhesion strength to the adherend and operable time.
- the amount is preferably from 00001 to 1 part by weight.
- the lower limit it is more preferably 0.0001 part by weight or more, further preferably 0.00025 part by weight or more, and particularly preferably 0.0005 part by weight or more.
- the upper limit is more preferably 0.1 parts by weight or less, and further preferably 0.005 parts by weight or less.
- the benzotriazole compound and the benzimidazole compound (c) are represented by the following general formulas (1) and (2), 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 group represented by R 1 to R 8 may be linear, branched or cyclic, and preferably has 1 to 10 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl Neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptanyl group, n-octyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, Examples thereof include a cyclononyl group and an n-decyl group. Among these, a methyl
- the aryl group represented by R 1 to R 8 preferably has 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
- the alkoxy group represented by R 1 to R 8 may be linear, branched or cyclic, and preferably has 1 to 8 carbon atoms. Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, 2-ethylhexyloxy group Etc.
- the alkenyl group represented by R 1 to R 8 may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. Examples include vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like.
- Examples of the aralkyl group represented by R 1 to R 8 include 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). Specific examples include a benzyl group.
- Examples of the halogen atom represented by R 1 to R 8 include 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 compound and the benzimidazole compound (c) may be used alone or in combination.
- Specific examples of the benzotriazole compound and the benzimidazole compound (c) include 1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, Examples include 5,6-dimethylbenzimidazole.
- 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferable from the viewpoint of color tone and storage stability of the composition.
- the compounding amount of the compound (c) is 0.
- the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight from the viewpoint of adhesion strength to the adherend and operable time. 01 to 10 parts by weight is preferred, 0.05 to 5 parts by weight is more preferred, and 0.5 to 3 parts by weight is most preferred.
- the compounding ratio of the compound (c) and the copper compound (b) is preferably 1: 0.00001 to 1: 0.01 in terms of molar ratio, and is 1: 0.0001 to 1: 0.005. Is more preferable.
- the compounding ratio of the copper compound (b) and the compound (c) is within this range, more excellent mechanical strength can be obtained while suppressing discoloration due to hydrogen sulfide.
- the characteristics useful for dental use can be improved by further blending a specific optional component with the dental curable composition of the present invention.
- optional components include a polymerizable monomer component (f) that does not contain an acidic group; an aromatic sulfinate (d), an organic peroxide as a polymerization initiator system component.
- E inorganic peroxide
- i amine-based reducing agent
- j reducing inorganic compound
- g water-soluble organic solvent
- filler (k) as other components
- aromatic sulfinate (d) examples include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfin.
- Lidine such as 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, naphthalenesulfinic acid, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt, calcium salt, strontium salt, iron salt And zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts.
- lithium salt, sodium salt, potassium salt, magnesium of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid in terms of curability and storage stability of the composition
- Salts and calcium salts are preferable, and lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferable.
- the dental curable composition of the present invention can ensure a longer operating margin, and when applied to the dentin, the aromatic sulfinate (d) is the dentine. Since it dissolves in the water on the surface, it is possible to further enhance the polymerization curability in the adhesive interface and the resin impregnated layer.
- the aromatic sulfinate (d) preferably has a solubility in water of 1 mg / 100 mL or more at room temperature (25 ° C.).
- 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 diameter is preferably 0.01 ⁇ m or more. That is, the average particle diameter when dispersed in powder is preferably in the range of 0.01 to 500 ⁇ m, more preferably in the range of 0.01 to 100 ⁇ m.
- the average particle diameter of the aromatic sulfinate (d) refers to the volume average particle diameter.
- the volume average particle diameter is, for example, image analysis software (based on an electron micrograph of 100 or more particles). For example, it can be calculated by performing image analysis using Mac-View (manufactured by Mountec).
- the shape in the case of dispersing the aromatic sulfinate (d) in powder includes various shapes such as a spherical shape, a needle shape, a plate shape, and a crushed shape, but is not particularly limited.
- the aromatic sulfinate (d) can be produced as a fine powder by a conventionally known method such as a pulverization method or a freeze-drying method.
- the blending amount of the aromatic sulfinate (d) is when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight from the viewpoint of the adhesive strength with the adherend and the operable time. In addition, 0.01 to 20 parts by weight is preferable. When the blending amount is less than 0.01 parts by weight, the adhesion strength of the resulting composition to the adherend may be reduced, more preferably 0.05 parts by weight or more, and still more preferably 0.1 parts by weight. Part or more, even more preferably 0.2 part by weight or more, even more preferably 0.25 part by weight or more, and most preferably 0.3 part by weight or more.
- the handleability of the resulting dental curable composition and the mechanical strength of the resulting cured product may be lowered, more preferably 15 parts by weight or less, More preferably, it is 10 parts by weight or less, and most preferably 5 parts by weight or less.
- the mechanical strength of the obtained cured product can be further improved.
- the organic peroxide (e) is not particularly limited, and any known one can be used.
- Representative organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and the like.
- hydroperoxide and peroxyester are particularly preferable, and peroxyester is most preferable from the viewpoint of storage stability of the resulting dental curable composition.
- One type of organic peroxide (e) may be used alone, or a plurality of types may be used in combination.
- the hydroperoxide includes cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3, Examples thereof include 3-tetramethylbutyl hydroperoxide.
- any known peroxy group (—OO— group) having an acyl group on one side and a hydrocarbon group (or a group similar thereto) on the other side can be used without any limitation.
- Specific examples include ⁇ , ⁇ -bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1 , 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoyl
- t-butyl peroxymaleic acid t-butyl peroxy 3,5,5-trimethylhexanoate
- t-butyl peroxybenzoate t-butyl Peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, and t-butyl peroxyacetate are preferable, and t-butyl peroxybenzoate is more preferable.
- ketone peroxide examples include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
- Peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butyl) Peroxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t-butylper) Oxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, and the like.
- Dialkyl peroxides include ⁇ , ⁇ -bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylcumi. Examples include ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3, and the like.
- Diacyl peroxide includes isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide M-toluoyl benzoyl peroxide and benzoyl peroxide.
- Peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and the like.
- the content of the organic peroxide (e) is 100 parts by weight with respect to the total amount of the polymerizable monomer components in the dental curable composition, from the viewpoint of the adhesive strength with the adherend and the operable time.
- the amount is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 3 parts by weight, and still more preferably 0.025 to 1 part by weight.
- Examples of the inorganic peroxide (h) include peroxodisulfate and peroxodiphosphate, and among these, peroxodisulfate is preferable from the viewpoint of redox reactivity.
- Specific examples of peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.
- the above peroxodisulfate may be used alone or in combination of two or more.
- sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are preferable.
- the inorganic peroxide (h) is preferably blended in a powder form in the dental curable composition because high storage stability of the dental curable composition is obtained.
- the average particle size of the powdered inorganic peroxide (h) is preferably in the range of 0.01 to 50 ⁇ m, and more preferably in the range of 0.1 to 20 ⁇ m.
- the powdered inorganic peroxide (h) has such an average particle diameter, the powdered inorganic peroxide (h) is efficiently dissolved in the water on the tooth surface at the adhesion interface, and the adhesion is improved. It is possible to selectively enhance the polymerization curability inside the resin-impregnated layer formed on the adhesive interface and the tooth.
- the average particle size can be measured in the same manner as the average particle size of the aromatic sulfinate (d).
- the shape of the powdered inorganic peroxide (h) includes various shapes such as a spherical shape, a needle shape, a plate shape, and a crushed shape, but is not particularly limited.
- the powdery inorganic peroxide (h) can be produced by a conventionally known method such as a pulverization method, a freeze-drying method, or a reprecipitation method.
- a pulverization method a freeze-drying method
- a reprecipitation method a method for producing the powdered inorganic peroxide (h)
- the pulverization method and the freeze-drying method are preferable, and the pulverization method is more preferable from the viewpoint of the average particle diameter of the obtained powder.
- the blending amount of the inorganic peroxide (h) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition of the present invention.
- the blending amount is less than 0.01 parts by weight, the adhesive strength may decrease.
- the blending amount exceeds 10 parts by weight, the adhesive strength and the mechanical strength of the cured product may be reduced.
- the amine-based reducing agent (i) is roughly classified into an aromatic amine and an aliphatic amine. In the present invention, either an aromatic amine or an aliphatic amine may be used. One type of amine reducing agent (i) may be used alone, or a plurality of types may be used in combination.
- aromatic secondary amine a known aromatic secondary amine, aromatic tertiary amine, or the like may be used.
- aromatic secondary amine or aromatic tertiary amine 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-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis ( 2-hydroxyethyl) -3,5-di-t-butylaniline, N, N-dimethylani
- aliphatic amine examples include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N— Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) Examples thereof include tertiary aliphatic amines such as acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine.
- primary aliphatic amines such as n-butylamine, n-hexyl
- tertiary aliphatic amines are preferable from the viewpoint of redox reactivity, and among them, N-methyldiethanolamine, triethanolamine, and 2- (dimethylamino) ethyl methacrylate are particularly preferable.
- a preferable blending amount of the amine reducing agent (i) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition of the present invention. 02 to 5 parts by weight is more preferable, and 0.05 to 2 parts by weight is most preferable.
- the blending amount is less than 0.01 parts by weight, the adhesive strength of the resulting dental curable composition to the tooth substance may be reduced.
- the blending amount exceeds 10 parts by weight, the color stability of the resulting dental curable composition may be lowered.
- Examples of the reducing inorganic compound (j) containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. Among them, sulfites, heavy sulfates, and the like. Sulphites are preferred, and specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.
- the reducing inorganic compound (j) containing sulfur may be used alone or in combination of two or more.
- the dental curable composition of the present invention can ensure a longer operating margin, and when applied to the tooth, the reducing inorganic compound (j) is the surface of the tooth. Therefore, it is possible to further enhance the polymerization curability in the adhesion interface portion and the resin impregnated layer.
- the reducing inorganic compound (j) preferably has a solubility in water at room temperature (25 ° C.) of 1 mg / 100 mL or more.
- 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 diameter is preferably 0.01 ⁇ m or more.
- the average particle diameter when dispersed in powder is preferably in the range of 0.01 to 500 ⁇ m, more preferably in the range of 0.01 to 100 ⁇ m.
- the said average particle diameter can be measured similarly to the average particle diameter of said aromatic sulfinate (d).
- the shape when the reducing inorganic compound (j) is dispersed in powder includes various shapes such as a spherical shape, a needle shape, a plate shape, and a crushed shape, but is not particularly limited.
- the reducing inorganic compound (j) can be made into fine powder by a conventionally known method such as a pulverization method or a freeze-drying method.
- the polymerization initiator system component of the dental curable composition of the present invention contains components (b), (c), (d), (h), (i), and (j), dental
- dental The adhesive strength of the curable composition for teeth to the tooth is particularly high.
- the blending amount of the reducing inorganic compound (j) is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components in the dental curable composition of the present invention. 05 to 10 parts by weight is more preferable, and 0.1 to 5 parts by weight is most preferable. When the blending amount is less than 0.01 parts by weight, the adhesive strength of the resulting dental curable composition to the tooth substance may be reduced. On the other hand, when the blending amount exceeds 15 parts by weight, the mechanical strength of the cured product of the resulting dental curable composition may be reduced.
- the polymerizable monomer (f) having no acidic group a radical polymerizable monomer having a polymerizable group is preferable.
- the polymerizable group is a (meth) acryl group and / or Or it is preferable that it is a (meth) acrylamide group.
- the dental curable composition of the present invention is used in the oral cavity, the oral cavity is a moist environment and the polymerizable group may be detached by hydrolysis or the like.
- the polymerizable group is preferably a methacryl group and / or a methacrylamide group.
- the polymerizable monomer (f) having no acidic group contributes to the improvement of the coating property, adhesiveness, and mechanical strength after curing of the composition.
- Examples of the polymerizable monomer (f) having no acidic group include the following water-soluble polymerizable monomers and hydrophobic polymerizable monomers.
- the water-soluble polymerizable monomer means one having a solubility in water at 25 ° C. of 10% by weight or more. Those having a solubility of 30% by weight or more are preferred, and those having solubility in water at an arbitrary ratio at 25 ° C. are more preferred.
- the water-soluble polymerizable monomer promotes the penetration of the component into the tooth, and also penetrates the tooth itself and adheres to the organic component (collagen) in the tooth.
- water-soluble polymerizable monomers examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2, Examples include 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonium ethyl (meth) acryl chloride, and polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups).
- hydrophobic polymerizable monomer examples include crosslinkable polymerizable monomers having a solubility in water at 25 ° C. of less than 10% by weight, and include aromatic compound-based bifunctional polymerizable monomers and aliphatic compounds. Examples thereof include a compound-based bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
- the hydrophobic polymerizable monomer improves the handleability of the composition, the mechanical strength after curing, and the like.
- aromatic compound-based bifunctional polymerizable monomers examples include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxy) Phenyl) 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) acryloyloxypentaethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydi
- aliphatic compound-based bifunctional polymerizable monomers examples include glycerol di (meth) acrylate, erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di ( (Meth) acrylate, dipentaerythritol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanedioe Di (meth) acrylate, 1,6-he
- glycerol di (meth) acrylate triethylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate and 1,2- Bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane is 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 tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene)
- Examples include bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.
- the polymerizable monomer (f) having no acidic group may be used alone or in combination. May be blended.
- the above-mentioned hydrophobic polymerizable monomer and water-soluble polymerizable monomer are used as the polymerizable monomer (f) having no acidic group. It is preferable to use a monomer in combination.
- the amount of the water-soluble polymerizable monomer is preferably in the range of 10 to 90 parts by weight when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight. A range of ⁇ 70 parts by weight is more preferred, and a range of 30-60 parts by weight is most preferred.
- the blending amount of the hydrophobic polymerizable monomer is preferably 9 to 60 parts by weight when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight. More preferably, it is ⁇ 55 parts by weight, and further preferably 20-50 parts by weight.
- the dental curable composition of the present invention is used as a dental cement or a dental self-adhesive composite resin
- the above-mentioned hydrophobic polymerization is performed as a polymerizable monomer (f) having no acidic group.
- a water-soluble monomer and a water-soluble polymerizable monomer in combination.
- the amount of the water-soluble polymerizable monomer is preferably in the range of 1 to 50 parts by weight when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight. A range of ⁇ 40 parts by weight is more preferred, and a range of 5-30 parts by weight is most preferred.
- the blending amount of the hydrophobic polymerizable monomer is preferably 10 to 95 parts by weight and preferably 30 to 90 parts by weight in 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition. More preferably, it is 50 to 80 parts by weight.
- the polymerizable monomer (f) having no acidic group is an aromatic compound based on the handling properties, transparency, mechanical strength after curing, and the like of the resulting dental curable composition.
- These bifunctional polymerizable monomers are preferably used in combination with a water-soluble polymerizable monomer and / or an aliphatic compound-based bifunctional polymerizable monomer.
- the ratio in the case of using them together is not particularly limited, but when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by weight, the aromatic compound-based bifunctional polymerizable monomer Is preferably 30 to 80 parts by weight, more preferably 40 to 75 parts by weight, and even more preferably 50 to 70 parts by weight.
- the amount of the water-soluble polymerizable monomer is preferably 0 to 30 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 5 to 20 parts by weight.
- the blending amount of the aliphatic compound-based bifunctional polymerizable monomer is preferably 5 to 65 parts by weight, more preferably 7 to 50 parts by weight, and preferably 10 to 35 parts by weight. Further preferred.
- an organic solvent having a solubility in water at 25 ° C. of 5% by weight or more, more preferably 30% by weight or more, and most preferably an arbitrary ratio is soluble in water.
- a water-soluble organic solvent (g) having a boiling point of 100 ° C. or less under normal pressure is preferable, and specific examples thereof include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, , 2-diethoxyethane, tetrahydrofuran.
- One type of water-soluble organic solvent (g) may be blended, or a plurality of types may be blended.
- the amount of the water-soluble organic solvent (g) is preferably 200 parts by weight or less with respect to 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition, and is 5 to 100 parts by weight. More preferably, it is 10 to 60 parts by weight.
- the dental curable composition of the present invention contains water
- the water promotes the decalcification action on the tooth by the acidic group-containing polymerizable monomer (a). It is necessary to use water that does not substantially contain impurities that adversely affect adhesion, and distilled water or ion-exchanged water is preferable.
- the blending amount of water is excessive, the adhesive strength may decrease, and it is preferable to blend in the range of 40% by weight or less based on the total weight of the dental curable composition.
- the dental curable composition of the present invention contains a filler (k), operability, X-ray opacity, mechanical strength after curing, adhesion, and the like can be improved.
- the filler (k) include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.
- a filler (k) may mix
- silica As the inorganic filler, silica; minerals based on silica such as kaolin, clay, mica, mica; silica based, Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , BaO, La Examples thereof include ceramics and glasses containing 2 O 3 , SrO, ZnO, CaO, P 2 O 5 , Li 2 O, Na 2 O and the like.
- glass lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used.
- organic filler examples include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymer, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.
- composite fillers of inorganic fillers and organic fillers include inorganic fillers dispersed in organic fillers and inorganic / organic composite fillers in which inorganic fillers are coated with various polymers.
- the filler (k) may be used after surface treatment with a known surface treatment agent such as a silane coupling agent.
- Surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Examples are mercaptopropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane.
- the dental curable composition of the present invention is used as a dental adhesive, among the fillers (k), the primary particle diameter is 0.001 to 0.1 ⁇ m in terms of adhesive strength and applicability. Particulate silica is preferably used.
- the blending amount of the filler (k) is preferably 0 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight of the dental curable composition.
- the filler for the purpose of improving handleability, radiopacity, mechanical strength, etc.
- k is preferably blended in the range of 10 to 90% by weight based on the total weight of the dental curable composition.
- the lower limit 30% by weight or more is more preferable, 40% by weight or more is more preferable, and 50% by weight or more is most preferable.
- the upper limit is more preferably 85% by weight or less.
- the dental curable composition of the present invention contains the above-mentioned chemical polymerization type polymerization initiator system, but in order to obtain a dual cure type composition that starts polymerization even by light irradiation, the above-mentioned polymerization initiator is used.
- a conventionally known photopolymerization initiator may be further added to the dental curable composition of the present invention.
- conventionally known photopolymerization initiators include ⁇ -diketones, ketals, thioxanthones, acylphosphine oxides, and ⁇ -aminoacetophenones.
- ⁇ -diketones include camphorquinone, benzyl, and 2,3-pentanedione.
- ketals include benzyl dimethyl ketal and benzyl diethyl ketal.
- thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
- acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis (2,6-dimethoxy).
- Benzoyl) 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 Water-soluble acylphosphine oxide compounds trimethyl benzoyl ethoxyphenyl phosphine oxide and KOKOKU 3-57916 Patent Publication discloses the like.
- ⁇ -aminoacetophenones include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl) ) -Butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -propanone-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -pentanone-1.
- One type of photopolymerization initiator may be used alone, or a plurality of types may be used in combination.
- the blending amount of the photopolymerization initiator is preferably in the range of 0.005 to 10 parts by weight when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight. With respect to the lower limit, 0.01 parts by weight or more is more preferable, and 0.1 parts by weight or more is more preferable.
- the upper limit is more preferably 5 parts by weight or less.
- a photopolymerization initiator and a polymerization accelerator such as an aldehyde, a thiol compound, or an aminobenzoic acid ester compound may be used in combination.
- aldehydes include terephthalaldehyde and benzaldehyde derivatives.
- benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.
- thiol compound examples include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.
- aminobenzoic acid ester compounds include 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester. 4-N, N-dimethylaminobenzoic acid 2-[(meth) acryloyloxy] ethyl ester, 4-N, N-dimethylaminobenzophenone, butyl 4-dimethylaminobenzoate and the like.
- the amine-based reducing agent (i) described above also functions as a polymerization accelerator for the photopolymerization initiator.
- One type of polymerization accelerator may be used alone, or a plurality of types may be used in combination.
- the blending amount of the polymerization accelerator is preferably in the range of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight when the total amount of the polymerizable monomer components in the dental curable composition is 100 parts by weight. A range of parts is more preferred.
- the dental curable composition of the present invention may further contain a fluorine ion releasing substance for the purpose of imparting acid resistance to the tooth.
- Fluorine ion releasing substances include fluorine ion releasing polymers such as a copolymer of methyl methacrylate and methacrylic fluoride, fluorine ion releasing substances such as cetylamine hydrofluoride, and the above-described fluoro as an inorganic filler. Examples include aluminosilicate glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride and the like.
- the dental curable composition of the present invention may further contain additives such as a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber.
- additives such as a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber.
- antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan Good.
- the dental curable composition of the present invention can be configured not only as a one-part type, but also as a package type divided into two or more parts.
- the dental curable composition of the present invention includes a two-component composition in which the first agent and the second agent are composed of a liquid component and a liquid component, and a paste component (a liquid component and a liquid component). It is preferably used as a two-paste composition comprising a filler and a paste component.
- the dental curable composition of the present invention is configured as a packaged dental curable composition containing a first agent and a second agent
- the first agent is an acidic group-containing polymerizable monomer.
- A and a copper compound (b) are contained, and the second agent preferably contains a benzotriazole compound and / or a benzimidazole compound (c) and an aromatic sulfinate (d).
- the first agent further contains an organic peroxide (e).
- the organic peroxide (e) is a peroxy ester, excellent storage stability and high adhesion to enamel and a crown restoration material can be obtained, which is preferable.
- the mixing weight ratio of the first agent and the second agent is preferably 1:10 to 10: 1 in terms of curability of the resulting composition and a time that can be used for an adhesion operation (pot life).
- the benzotriazole compound and / or the benzimidazole compound (c) is blended with the composition containing the acidic group-containing polymerizable monomer (a) and the copper compound (b), the copper compound (b) As a result, the reaction of the copper compound with hydrogen sulfide is suppressed. As a result, the resulting composition has excellent curability, small discoloration of the cured product due to hydrogen sulfide in the oral environment, and excellent mechanical strength of the cured product. Since the catalytic activity of the copper compound (b) is improved, the compounding amount of the copper compound (b) can be made smaller than before, and the cured product by hydrogen sulfide in the oral cavity environment while obtaining good curability. It is also possible to obtain a composition with extremely small discoloration.
- the coexistence of the copper compound (b) with the benzotriazole compound and / or the benzimidazole compound (c) increases the catalytic activity of the copper compound (b) and decreases the reactivity with respect to hydrogen sulfide. This is because the benzotriazole compound and / or the benzimidazole compound (c) coordinate or interact with Cu of the compound (b).
- the present invention is also represented by the above general formula (1) as a polymerizable monomer component, an acidic group-containing polymerizable monomer (a), and a polymerization initiator system component.
- a dental curable composition comprising a benzotriazole compound and / or a copper salt of a benzimidazole compound (c) represented by the general formula (2).
- the dental curable composition comprises an aromatic sulfinate (d), an organic peroxide (e), and a polymerizable monomer (f) containing no acidic group. It is preferable to include at least one selected, and particularly preferable to include an aromatic sulfinate (d).
- the amount of copper salt of the benzotriazole compound and / or benzimidazole compound (c) is 0.00001 to 1 part by weight with respect to 100 parts by weight of the total amount of polymerizable monomer components in the dental curable composition. It is preferable that Regarding the lower limit, it is more preferably 0.0001 part by weight or more, further preferably 0.00025 part by weight or more, and particularly preferably 0.0005 part by weight or more.
- the upper limit is more preferably 0.1 parts by weight or less, and even more preferably 0.05 parts by weight or less.
- one form of the preferable dental curable composition of this invention is an acidic group containing polymeric monomer (a) and a polymerizable monomer (f) which does not have an acidic group as a polymerizable monomer component.
- polymerization initiator components inorganic peroxide (h), copper compound (b), amine-based reducing agent (i), aromatic sulfinate (d), and general formula (1) above
- the benzotriazole compound represented and / or the benzimidazole compound (c) represented by the general formula (2) are included.
- the preferred composition has not only excellent curability and an effect of suppressing discoloration of the cured product by hydrogen sulfide produced by caries bacteria, but also particularly excellent adhesion to dentin and enamel, and mechanical properties of the cured product. Especially excellent in strength.
- the preferred composition is particularly suitable for dental cement.
- the product form (particularly dental cement) is a one-component type
- the amine reducing agent (i) reacts with the inorganic peroxide (h) during storage and decomposes. May end up.
- the aromatic sulfinate (d) may react with the copper compound (b) and decompose. Therefore, in this case, the amount of radical generation is reduced.
- the product form using the preferred composition is preferably a two-part type containing the first agent and the second agent.
- the preferred composition also has a good operation margin time when it is made into a package type.
- the compounding ratio of the copper compound (b) and the aromatic sulfinate (d) is preferably 0.000003: 1 to 0.01: 1 in molar ratio, and 0.00003: More preferably, it is 1 to 0.005: 1.
- the compounding ratio of the copper compound (b) and the aromatic sulfinate (d) is within this range, excellent mechanical strength can be obtained while maintaining a practically preferable operation margin time.
- the blending amount of the copper compound (b) is preferably 0.000001 to 0.01% by weight in the total amount of the polymerization initiator components.
- the polymerization initiator component includes components (b) to (e) and (h) to (j) including optional components.
- the first agent contains the inorganic peroxide (h) and the second agent contains the amine-based reducing agent (i).
- the inorganic peroxide (h) and the amine-based reducing agent (i) are blended in different agents.
- the acidic group-containing polymerizable monomer (a) and the polymerizable monomer (f) having no acidic group may be contained in either or both of the first agent and the second agent, but are preserved. From the viewpoint of stability, the acidic group-containing polymerizable monomer (a) and the aromatic sulfinate (d) are preferably blended in different agents, and the first agent and the second agent are pasty.
- One of the agents contains the polymerizable monomer (a) and, if necessary, the polymerizable monomer (b), and the other agent is polymerized. It is preferable to contain a functional monomer (b).
- the compound (c) may be blended in either or both of the first agent and the second agent, but the copper compound (b) is an aromatic sulfinate (d) and a salt from the viewpoint of storage stability. It is preferable to mix with different agents.
- the first agent contains an acidic group-containing polymerizable monomer (a), an inorganic peroxide (h), and a copper compound (b), and the second agent contains an acidic group.
- the form which contains the polymerizable monomer (f) which does not have, an amine type reducing agent (i), an aromatic sulfinate (d), and a compound (c) is mentioned.
- the composition contains a reducing inorganic compound (j) containing sulfur
- the reducing inorganic compound (j) containing sulfur is preferably blended with the second agent.
- organic peroxide (i) it is preferable that organic peroxide (i) is mix
- the mixing weight ratio of the first agent and the second agent is preferably 1:10 to 5: 1 in terms of curability of the resulting composition and time (operation margin time) that can be used for adhesion operation.
- the product is dental cement
- a filler (k) to the first agent and / or the second agent from the viewpoint of the mechanical strength of the cured product.
- the above-mentioned preferable composition can exhibit high adhesive strength by using only the moisture contained in the tooth, even if it does not contain water. Moreover, when the above-mentioned preferable composition contains water, there exists a possibility that the storage stability of a composition may fall. For this reason, it is preferable that the above-mentioned preferable composition does not contain water substantially. “Contains substantially no water” means that water is not actively added in addition to the water originally contained in each component of the composition. Based on the weight, it is 1% by weight or less.
- the dental curable composition of the present invention is used as a dental cement, a dental adhesive, a dental self-adhesive composite resin, etc., in addition to the composition alone applied to the adhesive surface and used as a primer on the adhesive surface. It is also possible to apply and use the dental curable composition of the present invention after applying another composition.
- the dental curable composition of the present invention An example of a specific method for using the dental curable composition of the present invention will be described by taking a two-part product as an example.
- the first agent and the second agent are mixed to form one agent (dental curable composition of the present invention), and then applied to the tooth.
- the curing reaction also proceeds inside the wet body near the interface between the tooth and the dental curable composition.
- the dental curable composition of the present invention and the tooth substance are bonded.
- the case of applying to teeth will be described in detail as follows. That is, when filling and repairing the dental cavity, the dental cavity is cleaned by a conventional method, and then the dental curable composition of the present invention as one agent is filled into the dental cavity.
- the dental curable composition of the present invention is used as one agent after cleaning the abutment tooth or the cavity surface and the adhesion surface of the prosthesis. Is applied to at least one of the adhesion surface of the tooth cavity and the abutment tooth or the adhesion surface of the prosthesis, and bonded together.
- the tooth surface Prior to applying the dental curable composition of the present invention to the tooth surface, the tooth surface is conventionally known such as etching treatment with an acidic aqueous solution, modification treatment with a primer, simultaneous etching / modification treatment with a primer having etching ability, etc. The pretreatment may be performed.
- TPBSS Sodium 2,4,6-triisopropylbenzenesulfinate
- KPS potassium peroxodisulfate
- the average particle size was adjusted to 2.5 ⁇ m by grinding with a jet mill.
- the average particle size is calculated as a volume average particle size after performing image analysis using image analysis software (Mac-View; manufactured by Mountec) based on an electron micrograph of 100 or more particles. did.
- F1 Silane-treated quartz powder
- F2 Silane-treated barium glass powder
- R972 Silica (made by Nippon Aerosil Co., Ltd., trade name “Aerosil R972”)
- Alumina Nippon Aerosil Co., Ltd., trade name “Aluminum Oxide C”
- Silane-treated quartz powder (F1) and silane-treated barium glass powder (F2) are obtained according to the following production method.
- Silane-treated quartz powder F1: Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder having an average particle diameter of about 4.5 ⁇ m. 100 parts by weight of this quartz powder was subjected to surface treatment with 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain a silane-treated quartz powder.
- Silane-treated barium glass powder (F2): Barium glass (manufactured by STEC, product code “Raysorb E-3000”) was pulverized with a ball mill to obtain barium glass powder having an average particle size of about 2.4 ⁇ m. 100 parts by weight of this barium glass powder was subjected to surface treatment with 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain silane-treated barium glass powder.
- Examples 1 to 8 A first agent and a second agent having compositions shown in Table 1 (the numerical values in the table are parts by weight) are prepared, and the dental curable composition (the composition of the present invention) is prepared so that the weight ratio of these two agents is 1: 1.
- the product was divided into two drugs.
- the first agent was prepared by mixing components other than the filler and stirring to make a uniform solution, then kneading the filler and defoaming.
- the second agent is prepared by mixing ingredients other than 2,4,6-triisopropylbenzenesulfinic acid sodium (hereinafter referred to as TPBSS) and filler, stirring to obtain a uniform solution, and then kneading and removing TPBSS and filler.
- TPBSS 2,4,6-triisopropylbenzenesulfinic acid sodium
- the chromaticity in the L * , a * , b * color system was measured with a standard white plate placed behind the test piece, and these were designated L * 0 , a * 0 , b * 0 . These were the initial colors.
- this cured product was immersed in the following “hydrogen sulfide aqueous solution” and stored in a sealed container at 60 ° C. for 24 hours. Thereafter, the cured product is taken out and water droplets are wiped off.
- the chromaticity in the L * , a * , b * color system is measured in the same manner as in the initial color tone, and the color tone L * 1 , a * after immersion is measured . 1 and b * 1 .
- ⁇ E * ⁇ (L * 1 -L * 0) 2 + (a * 1 -a * 0) 2 + (b * 1 -b * 0) 2 ⁇ 1/2
- “Hydrogen sulfide aqueous solution” was prepared as follows. Sodium sulfide 9-hydrate (special grade reagent) 0.6955 g was dissolved in distilled water to prepare 2 ml of an aqueous sodium sulfide solution. Also, distilled water was added to 6.33 ml of 35 wt% concentrated hydrochloric acid to prepare 100 ml of diluted hydrochloric acid. 1 ml of the aqueous sodium sulfide solution was placed in a 10 ml sample tube, and 4 ml of the diluted hydrochloric acid was added thereto and shaken to generate hydrogen sulfide.
- the pH of the liquid (hydrogen sulfide aqueous solution) in the sample tube when hydrogen sulfide was generated was 7.0 to 7.7.
- a simple pH meter (trade name “Twin pH B-212”, manufactured by HORIBA, Ltd.) was used for pH measurement, but the pH of the liquid increased as hydrogen sulfide evolved.
- the discoloration test was started 10 minutes after mixing.
- the polymerized cured product was immersed in distilled water at 37 ° C. for 24 hours and stored, and then subjected to a bending test using this as a test piece.
- the bending strength was measured by performing a three-point bending test with a universal testing machine at a span of 20 mm and a crosshead speed of 1 mm / min. The average value of the bending strength for the five test pieces was taken as the bending strength of the sample.
- Examples 9 to 12, Comparative Examples 3 to 4 A first agent and a second agent having compositions shown in Table 2 (each value in the table is parts by weight) were prepared, and a two-pack type dental adhesive having a weight ratio of these two agents of 1: 1 was prepared.
- the first agent and the second agent were prepared by mixing components other than R972 and stirring to obtain a uniform solution, and then adding R972 and stirring.
- T2 the bonding operation possible time
- C2 color tone change
- the color tone of the obtained cured product was measured using a color difference meter (Nippon Denshoku: SE6000), and this was used as the initial value of the color tone.
- this cured product was immersed in the following “hydrogen sulfide aqueous solution” and stored in a sealed container at 60 ° C. for 24 hours. Thereafter, the cured product was taken out and water droplets were wiped off, and the color tone of the cured product was measured in the same manner as in the initial stage, and this was used as the color tone after immersion in hydrogen sulfide water.
- the difference ( ⁇ E * ) between the color tone after immersion in hydrogen sulfide water and the initial value was defined as discoloration.
- the “hydrogen sulfide aqueous solution” was prepared by a method similar to the method described in the color change (C1) of the cement cured product with hydrogen sulfide water.
- the dental curable compositions of the present invention produced in Examples 1 to 8 showed high curability despite the fact that the copper compound was contained in a trace amount, and discolored in hydrogen sulfide water. Was small.
- the dental curable composition prepared in Comparative Example 1 although the discoloration of the cured product in hydrogen sulfide water is small, the operable time exceeds 10 minutes and is longer than the actual use level (2 to 8 minutes). The curability was low.
- the comparative example 2 showed the outstanding sclerosis
- the dental curable compositions of the present invention produced in Examples 9 to 12 exhibit high curability despite the fact that the copper compound is contained in a trace amount, and are discolored in hydrogen sulfide water. Was small.
- the dental curable composition prepared in Comparative Example 3 although the discoloration of the cured product in hydrogen sulfide water is small, the operable time exceeds 10 minutes and is longer than the actual use level (2 to 8 minutes). The curability was low.
- the comparative example 4 showed the outstanding sclerosis
- the 1st agent and 2nd agent which show a composition in Table 3 were prepared, and the dental curable composition was divided into 2 agents so that the weight ratio of these 2 agents might be set to 1: 1.
- the first agent was prepared by mixing components other than the powdery components (filler and KPS) and stirring to obtain a uniform solution, and then kneading and defoaming the powdery components.
- the powdery component in the first agent was in a dispersed state in a powder state.
- the second agent was prepared by mixing components other than the powdery components (filler, TPBSS and sodium sulfite), stirring to obtain a uniform solution, and then kneading and defoaming the powdery components.
- the powdery component in the second agent was dispersed in a powdery state.
- These packaged dental curable compositions curable cement compositions
- operation margin adhesion to bovine enamel
- adhesion to bovine dentin adhesion to bovine dentin
- bending of hardened material The strength and the discoloration of the cured cement when the cured product was immersed in hydrogen sulfide water were examined. The results are shown in Table 3.
- the first agent and the second agent were mixed at a weight ratio of 1: 1 in a thermostatic chamber at 23 ° C., and mixed well with a spatula to make one agent.
- the time (operation margin time) from the mixing time to the time when the temperature starts to rise due to the start of curing of the paste was measured with a thermocouple (Okazaki Seisakusho) connected to a recorder (manufactured by Yokogawa Electric Corporation). Note that the operation allowance time suitable for actual use is 2 to 8 minutes.
- the cement composition was built up on one end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm), and the center of the round hole and the center of the stainless steel cylindrical rod were approximately Place the end face on the side where the cement composition was built up so as to match, and place it on a smooth surface (attachment surface) in a round hole, and press and bond a stainless steel cylindrical rod perpendicular to the smooth surface,
- a test sample was prepared. Five test samples were prepared. After removing the excess cement composition protruding from the periphery of the stainless steel cylindrical rod when pressed, the test sample was allowed to stand at room temperature for 30 minutes and immersed in distilled water.
- the test sample immersed in distilled water was allowed to stand for 24 hours in a thermostat maintained at 37 ° C.
- the tensile bond strength after leaving still at 37 degreeC for 24 hours was investigated.
- the tensile bond strength was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min.
- the tensile bond strength in the table is an average value of the measured values of five test samples.
- the cement composition was built up on one end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm), and the center of the round hole and the center of the stainless steel cylindrical rod were approximately Place the end face on the side where the cement composition was built up so as to match, and place it on a smooth surface (attachment surface) in a round hole, and press and bond a stainless steel cylindrical rod perpendicular to the smooth surface,
- a test sample was prepared. Five test samples were prepared. After removing the excess cement composition protruding from the periphery of the stainless steel cylindrical rod when pressed, the test sample was allowed to stand at room temperature for 30 minutes and immersed in distilled water.
- the test sample immersed in distilled water was allowed to stand for 24 hours in a thermostat maintained at 37 ° C.
- the tensile bond strength after leaving still at 37 degreeC for 24 hours was investigated.
- the tensile bond strength was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min.
- the tensile bond strength in the table is an average value of the measured values of five test samples.
- the curable compositions of the present invention used in Examples 13 to 21 provide curability and excellent adhesion to dentin and enamel, and are excellent in mechanical strength. Things were obtained. Moreover, although the copper compound was used, discoloration of the cured product due to hydrogen sulfide produced by caries bacteria was suppressed, and the operation margin time was also good.
- the dental curable composition of the present invention can be used as a dental adhesive, dental cement, composite resin, self-adhesive composite resin, sealant, dental room temperature polymerization resin, and the like.
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Abstract
Description
MDP:10-メタクリロイルオキシデシルジハイドロジェンホスフェート
4-META:4-メタクリロイルオキシエチルトリメリテートアンハイドライド
CAA:アセチルアセトン銅(II)
CA:酢酸銅(II)
BTA:1H-ベンゾトリアゾール
MBTA:5-メチル-1H-ベンゾトリアゾール
BIA:ベンゾイミダゾール
TPBSS:2,4,6-トリイソプロピルベンゼンスルフィン酸ナトリウム
<パーオキシエステル>
BPB:t-ブチルパーオキシベンゾエート
BEC:t-ブチルパーオキシ2-エチルヘキシルモノカーボネート
CHP:クメンハイドロパーオキサイド
KPS:ペルオキソ二硫酸カリウム:ジェットミルにより粉砕することで、平均粒子径を2.5μmに調整した。また、本実施例において平均粒子径は、粒子100個以上の電子顕微鏡写真をもとに画像解析ソフト(Mac-View;マウンテック社製)を用いて画像解析を行った後に体積平均粒子径として算出した。
DEPT:N,N-ジ(2-ヒドロキシエチル)-p-トルイジン
亜硫酸ナトリウム:振動ボールミルにて粉砕を行うことで、平均粒子径を6.1μmに調整した。
<疎水性の重合性単量体>
Bis-GMA:2,2-ビス〔4-(3-メタクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン
D2.6E:2,2-ビス(4-メタクリロイルオキシポリエトキシフェニル)プロパン
GDMA:グリセロールジメタクリレート
NPG:ネオペンチルグリコールジメタクリレート
HEMA:2-ヒドロキシエチルメタクリレート
CQ:dl-カンファーキノン
TMDPO:2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド
PDE:N,N-ジメチルアミノ安息香酸エチルエステル(光重合開始剤の重合促進剤)
BHT:2,6-ジ-t-ブチル-4-メチルフェノール
F1:シラン処理石英粉
F2:シラン処理バリウムガラス粉
R972:シリカ(日本アエロジル社製、商品名「アエロジルR972」)
アルミナ:日本アエロジル社製、商品名「アルミニウムオキサイドC」
石英(MARUWA QUARTZ製)をボールミルで粉砕し、平均粒子径が約4.5μmの石英粉を得た。この石英粉100重量部に対して、通法により3重量部の3-メタクリロイルオキシプロピルトリメトキシシランで表面処理を行い、シラン処理石英粉を得た。
バリウムガラス(エステック社製、商品コード「Raysorb E-3000」)をボールミルで粉砕し、平均粒子径が約2.4μmのバリウムガラス粉を得た。このバリウムガラス粉100重量部に対して、通法により3重量部の3-メタクリロイルオキシプロピルトリメトキシシランで表面処理を行い、シラン処理バリウムガラス粉を得た。
表1に組成(表の各数値は重量部)を示す第1剤及び第2剤を調製し、これら2剤の重量比が1:1となるように歯科用硬化性組成物(本発明組成物)を2剤に分包した。第1剤は、フィラー以外の成分を調合後、攪拌して均一な溶液とした後、フィラーを練り込み脱泡して作製した。また、第2剤は、2,4,6-トリイソプロピルベンゼンスルフィン酸ナトリウム(以下、TPBSS)及びフィラー以外の成分を調合後、攪拌して均一な溶液とした後、TPBSS及びフィラーを練り込み脱泡して作製した。これらの分包した歯科用硬化性組成物について、下記に示す方法により、セメント操作可能時間(T1)、硫化水素水によるセメント硬化物の色調変化(C1)、及びセメント硬化物の曲げ強さ(S1)について調べた。結果を表1に示す。
表1に組成を示す第1剤及び第2剤を調製し、これら2剤の重量比が1:1となるように歯科用硬化性組成物(比較組成物)を2剤に分包した。第1剤及び第2剤は、フィラー以外の成分を調合後、攪拌して均一な溶液とした後、フィラーを練り込み脱泡して作製した。これらの分包した歯科用硬化性組成物について、実施例1~8と同様にセメント操作可能時間(T1)、硫化水素水によるセメント硬化物の色調変化(C1)、及びセメント硬化物の曲げ強さ(S1)について調べた。結果を表1に示す。
25℃の恒温室中において第1剤と第2剤を重量比1:1で混合し、ヘラにてよく混和して1剤とした。混合した時刻からペーストの硬化開始によって温度が上昇し始める時刻までの時間(操作可能時間)を記録計(横河電機社製)に接続した熱電対(岡崎製作所社製)により測定した。なお、実使用に適した操作可能時間は、2~8分である。
第1剤と第2剤を重量比1:1で混合し、1mm厚、直径1.5cmの円盤状の金型に充填して37℃において1時間静置し硬化物を作製した。得られた硬化物の色調をJIS-Z8729に記載の条件を満足する分光色差計(日本電色工業社製、商品名「SE 6000」)を用いてD65光源、測色視野2度の条件において、試験片の背後に標準白板を置いた状態でL*、a*、b*表色系での色度を測定し、これらをL* 0、a* 0、b* 0とした。これらを初期の色調とした。次に、この硬化物を以下の「硫化水素水溶液」に浸漬し、密閉容器中60℃において24時間保管した。その後、硬化物を取り出して水滴をふき取り、初期の色調と同様の手法でL*、a*、b*表色系での色度を測定し、これらを浸漬後の色調L* 1、a* 1、b* 1とした。硫化水素との反応による変色は、サンプルを清浄な大気中に放置すると減少する傾向があるので、保存後の色度の測定は、サンプルを液から大気中に取り出してから10分以内に行うようにした。得られたそれぞれの値を下式に代入し、変色の指標であるΔE*を求めた。
ΔE*={(L* 1-L* 0)2+(a* 1-a* 0)2+(b* 1-b* 0)2}1/2
スライドガラス板上にポリエステルフィルムを敷設し、その上に縦2mm×横25mm×深さ2mmのステンレス製の型枠を載置した。次いで、第1剤と第2剤を重量比1:1で混練して得た組成物を型枠内に充填し、型枠内の組成物の表面をポリエステルフィルムを介してスライドガラスで圧接し、2枚のスライドガラスを幅25mmのダブルクリップを用いて固定した。ダブルクリップで固定したサンプルを37℃の恒温器内で1時間静置して重合硬化させた後、サンプルを恒温器から取り出し、型枠から組成物の重合硬化物を取り外した。重合硬化物を37℃の蒸留水中に24時間浸漬して保管した後、これを試験片として曲げ試験を行った。曲げ強さは、万能試験機により、スパン20mm、クロスヘッドスピード1mm/分で3点曲げ試験を行って測定した。5個の試験片についての曲げ強さの平均値をその試料の曲げ強さとした。
表2に組成(表の各数値は重量部)を示す第1剤及び第2剤を調製し、これら2剤の重量比が1:1の2液型の歯科用接着材を作製した。第1剤及び第2剤は、R972以外の成分を調合後、攪拌して均一な溶液とした後、R972を加え、撹拌して作製した。これらの2液型の歯科用接着材について、下記に示す方法により、ボンド操作可能時間(T2)、及び硫化水素水によるボンド硬化物の色調変化(C2)について調べた。結果を表2に示す。
25℃の恒温室中において、直径1cm、深さ5mmの半球状の樹脂製容器に第1剤及び第2剤をそれぞれ0.1g入れ、ヘラにてよく混和して1剤とした。混和後ただちにこの液剤中に、記録計(横河電機社製)に接続した熱電対(岡崎製作所社製)を挿入し、重合硬化反応に伴う温度変化を記録計にて記録し、硬化時間(混和後、発熱ピークが立ち上がるまでの時間)を求めた。なお、実使用に適した操作可能時間は、2~8分である。
第1剤と第2剤を重量比1:1で混合し、これを1枚のスライドガラス上に滴下した。次いで、歯科用エアーシリンジを用いて歯科用接着材の流動性が無くなるまで乾燥した後、厚さ0.1mmの金属スペーサーを介して2枚目のスライドガラスをかぶせた。そのスライドガラスの上から、歯科用光照射器「JETLITE3000」を用いて20秒間光照射して、硬化させた。光照射後、2枚のスライドガラスを取り外し、厚さ0.1mm、直径約1cmの硬化物を得た。得られた硬化物の色調を色差計(日本電色:SE6000)を用いて測定し、これを色調の初期値とした。次に、この硬化物を以下の「硫化水素水溶液」に浸漬し、密閉容器中60℃において24時間保管した。その後、硬化物を取り出して水滴をふき取り、硬化物の色調を初期と同様に測定し、これを硫化水素水浸漬後の色調とした。硫化水素水浸漬後の色調と初期値との差(ΔE*)を変色とした。なお、「硫化水素水溶液」は、硫化水素水によるセメント硬化物の色調変化(C1)に記載した方法と同様の方法で調製した。
表3に組成を示す第1剤及び第2剤を調製し、これら2剤の重量比が1:1となるように歯科用硬化性組成物を2剤に分包した。第1剤は、粉末状成分(フィラー及びKPS)以外の成分を調合後、攪拌して均一な溶液とした後、粉末状成分を練り込み脱泡して作製した。第1剤中の粉末状成分は、粉末状態で分散した状態であった。また、第2剤は、粉末状成分(フィラー、TPBSS及び亜硫酸ナトリウム)以外の成分を調合後、攪拌して均一な溶液とした後、粉末状成分を練り込み脱泡して作製した。第2剤中の粉末状成分は、粉末状に分散した状態であった。これらの分包した歯科用硬化性組成物(硬化性セメント組成物)について、下記に示す方法により、操作余裕時間、牛歯エナメル質に対する接着性、牛歯象牙質に対する接着性、硬化物の曲げ強さ、及び硬化物の硫化水素水浸漬時のセメント硬化物の変色について調べた。結果を表3に示す。
23℃の恒温室中において第1剤と第2剤を重量比1:1で混合し、ヘラにてよく混和して1剤とした。混合した時刻からペーストの硬化開始によって温度が上昇し始める時刻までの時間(操作余裕時間)を記録計(横河電機社製)に接続した熱電対(岡崎製作所社製)により測定した。なお、実使用に適した操作余裕時間は、2~8分である。
ウシ下顎前歯の唇面を流水下にてシリコン・カーバイド紙で研磨してエナメル質の平坦面を露出させた。露出した平坦面を流水下にて#1000のシリコン・カーバイド紙でさらに研磨した。研磨後、表面の水をエアブローすることで乾燥した。乾燥後の平滑面に、直径3mmの丸穴を有する厚さ約150μmの粘着テープを貼着し、接着面積を規制した。分包した硬化性組成物の第1剤と第2剤とを重量比1:1で混練してセメント組成物を調製した。そのセメント組成物を、ステンレス製円柱棒(直径7mm、長さ2.5cm)の一方の端面(円形断面)に築盛し、上記の丸穴の中心と上記のステンレス製円柱棒の中心とが略一致するように、セメント組成物を築盛した側の端面を丸穴内の平滑面(被着面)に載置し、その平滑面に対して垂直にステンレス製の円柱棒を押し付けて接着して、供試サンプルを作製した。供試サンプルは、5個作製した。押し付けた際にステンレス製の円柱棒の周囲からはみ出た余剰のセメント組成物を除去した後、供試サンプルを、30分間室温で静置し、蒸留水に浸漬した。蒸留水に浸漬した供試サンプルを、37℃に保持した恒温器内に24時間静置した。この供試サンプルについて、37℃24時間静置後の引張接着強さを調べた。引張接着強さは、万能試験機(島津製作所社製)にてクロスヘッドスピードを2mm/分に設定して測定した。表中の引張接着強さは、5個の供試サンプルについての測定値の平均値である。
ウシ下顎前歯の唇面を流水下にてシリコン・カーバイド紙で研磨して象牙質の平坦面を露出させた。露出した平坦面を流水下にて#1000のシリコン・カーバイド紙でさらに研磨した。研磨後、表面の水をエアブローすることで乾燥した。乾燥後の平滑面に、直径3mmの丸穴を有する厚さ約150μmの粘着テープを貼着し、接着面積を規制した。分包した硬化性組成物の第1剤と第2剤とを重量比1:1で混練してセメント組成物を調製した。そのセメント組成物を、ステンレス製円柱棒(直径7mm、長さ2.5cm)の一方の端面(円形断面)に築盛し、上記の丸穴の中心と上記のステンレス製円柱棒の中心とが略一致するように、セメント組成物を築盛した側の端面を丸穴内の平滑面(被着面)に載置し、その平滑面に対して垂直にステンレス製の円柱棒を押し付けて接着して、供試サンプルを作製した。供試サンプルは、5個作製した。押し付けた際にステンレス製の円柱棒の周囲からはみ出た余剰のセメント組成物を除去した後、供試サンプルを、30分間室温で静置し、蒸留水に浸漬した。蒸留水に浸漬した供試サンプルを、37℃に保持した恒温器内に24時間静置した。この供試サンプルについて、37℃24時間静置後の引張接着強さを調べた。引張接着強さは、万能試験機(島津製作所社製)にてクロスヘッドスピードを2mm/分に設定して測定した。表中の引張接着強さは、5個の供試サンプルについての測定値の平均値である。
前記のセメント硬化物の曲げ強さ(S1)と同様にして評価した。
前記の硫化水素水によるセメント硬化物の色調変化(C1)と同様にして評価した。
Claims (23)
- さらに芳香族スルフィン酸塩(d)を含む請求項1に記載の歯科用硬化性組成物。
- さらに酸性基を含まない重合性単量体(f)を含む請求項1又は2に記載の歯科用硬化性組成物。
- 重合性単量体成分の総量100重量部に対し、前記銅化合物(b)を0.00001~1重量部含む請求項1~3のいずれか1項に記載の歯科用硬化性組成物。
- 前記酸性基含有重合性単量体(a)、及び前記銅化合物(b)を含有する第1剤と、前記ベンゾトリアゾール化合物及び/又はベンゾイミダゾール化合物(c)、並びに芳香族スルフィン酸塩(d)を含有する第2剤とに分包された請求項2~4のいずれか1項に記載の歯科用硬化性組成物。
- さらに第1剤に有機過酸化物(e)を含む請求項5に記載の歯科用硬化性組成物。
- 前記有機過酸化物(e)が、パーオキシエステルである請求項6に記載の歯科用硬化性組成物。
- 重合性単量体成分として、前記酸性基含有重合性単量体(a)、及び酸性基を有しない重合性単量体(f)を含み、重合開始剤系成分として、無機過酸化物(h)、前記銅化合物(b)、アミン系還元剤(i)、芳香族スルフィン酸塩(d)、並びに前記ベンゾトリアゾール化合物及び/又はベンゾイミダゾール化合物(c)を含む請求項1に記載の歯科用硬化性組成物。
- 重合性単量体成分の総量100重量部に対し、前記銅化合物(b)を0.00001~1重量部含む請求項8に記載の歯科用硬化性組成物。
- 前記酸性基含有重合性単量体(a)、前記無機過酸化物(h)、及び前記銅化合物(b)を含有する第1剤と、前記酸性基を有しない重合性単量体(f)、前記アミン系還元剤(i)、前記芳香族スルフィン酸塩(d)、並びに前記ベンゾトリアゾール化合物及び/又はベンゾイミダゾール化合物(c)を含む第2剤とに分包された請求項8又は9に記載の歯科用硬化性組成物。
- さらに、重合開始剤系成分として、第2剤に硫黄を含有する還元性無機化合物(j)を含む請求項10に記載の歯科用硬化性組成物。
- さらに、重合開始剤系成分として、第1剤に有機過酸化物(i)を含む請求項10又は11に記載の歯科用硬化性組成物。
- 前記有機過酸化物(i)が、パーオキシエステルである請求項12に記載の歯科用硬化性組成物。
- 前記無機過酸化物(h)が、平均粒子径0.01~50μmの粉末状である請求項8~13のいずれか1項に記載の歯科用硬化性組成物。
- 前記酸性基含有重合性単量体(a)の配合量が、重合性単量体成分の総量100重量部中において1~50重量部である請求項8~14のいずれか1項に記載の歯科用硬化性組成物。
- 前記無機過酸化物(h)の配合量が、重合性単量体成分の総量100重量部に対して0.01~10重量部である請求項8~15のいずれか1項に記載の歯科用硬化性組成物。
- 前記アミン系還元剤(i)の配合量が、重合性単量体成分の総量100重量部に対して0.01~10重量部である請求項8~16のいずれか1項に記載の歯科用硬化性組成物。
- 前記芳香族スルフィン酸塩(d)の配合量が、重合性単量体成分の総量100重量部に対して0.1~20重量部である請求項8~17のいずれか1項に記載の歯科用硬化性組成物。
- 前記銅化合物(b)と前記芳香族スルフィン酸塩(d)の配合比が、モル比で0.000003:1~0.01:1である請求項8~18のいずれか1項に記載の歯科用硬化性組成物。
- 前記ベンゾトリアゾール化合物及び/又はベンゾイミダゾール化合物(c)と前記銅化合物(b)との配合比が、モル比で1:0.00001~1:0.01である請求項8~19のいずれか1項に記載の歯科用硬化性組成物。
- 前記銅化合物(b)の配合量が、重合開始剤系成分の総量において0.000001~0.01重量%である請求項8~20のいずれか1項に記載の歯科用硬化性組成物。
- さらに芳香族スルフィン酸塩(d)を含む請求項22に記載の歯科用硬化性組成物。
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CN103260582A (zh) | 2013-08-21 |
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US20130274426A1 (en) | 2013-10-17 |
JPWO2012086189A1 (ja) | 2014-05-22 |
US9125802B2 (en) | 2015-09-08 |
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EP2656831A1 (en) | 2013-10-30 |
EP2656831B1 (en) | 2016-05-11 |
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