WO2009084586A1 - 歯科用セメント - Google Patents
歯科用セメント Download PDFInfo
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- WO2009084586A1 WO2009084586A1 PCT/JP2008/073601 JP2008073601W WO2009084586A1 WO 2009084586 A1 WO2009084586 A1 WO 2009084586A1 JP 2008073601 W JP2008073601 W JP 2008073601W WO 2009084586 A1 WO2009084586 A1 WO 2009084586A1
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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 dental cement. More specifically, the present invention relates to a dental cement that is excellent in removability when temporarily removing with a light irradiator a surplus cement that protrudes from a margin when a dental restoration and a restoration for a crown are bonded to each other. .
- Tooth that has lost its function due to caries or accidents is repaired by fixing a dental restoration material made of metal or ceramics called an inlay or crown to the tooth, for example, to fix the dental restoration material to the tooth.
- a dental restoration material made of metal or ceramics called an inlay or crown
- an adhesive called dental cement.
- a slight excess of dental cement is applied to the inner wall of the dental restoration material and pressed against the dental material.
- a method is adopted in which an excessive amount of dental cement protrudes from a joint portion (hereinafter, also referred to as a margin portion) between a tooth and a crown restorative material, and the excess cement that protrudes is removed.
- the dental cement is provided as a paste-like composition having a high fluidity so that it can be easily applied to a restoration material for a crown and an appropriate surplus is appropriately produced from the margin portion. Further, if the excess cement is not completely removed, not only the aesthetic property is inferior, but also the cement that protrudes and hardens may damage the tissue in the oral cavity. Normally, this excess cement is removed using a dental short needle or the like, but it is difficult to remove with a short needle in a highly fluid state where the cement is not hardened at all. Accordingly, the excess cement is removed in a state where the cement is completely cured or in a state where the fluidity is lost to some extent due to the progress of curing (semi-cured state).
- Dental cements are classified into a plurality of types according to their components and curing modes, such as glass ionomer cements, resin reinforced glass ionomer cements, and resin cements, and each is put to practical use.
- Glass ionomer cement consists of a powder that elutes polyvalent metal ions and an aqueous solution of polycarboxylic acid, and the polyvalent metal ions and polycarboxylic acid that elute when this powder and aqueous solution are mixed are chelate-crosslinked. To cure.
- Such cement generally has a feature that it is easy to operate because it does not require any pretreatment of the tooth, and is excellent in removal of excess cement.
- the glass ionomer cement is excellent in the removal of excess cement because the mechanical strength of the completely hardened cement cured body is lower than that of the resin cement. This is because it is possible to break the body.
- glass ionomer cement has the above-mentioned advantages, but has a problem in terms of durability (reliability) of the cement itself. Furthermore, glass ionomer cements have a problem that physical properties such as mechanical strength are lowered when they come into contact with water such as saliva during curing.
- the cured product remains the main component of a chelate compound (ionomer) of a polycarboxylic acid and a polyvalent metal ion.
- the mechanical strength is lower than that of the resin cement mainly composed of, and the reliability is not sufficient.
- a resin-reinforced glass ionomer cement mainly composed of a polymer of a radical polymerizable monomer and having a mechanical strength closer to that of a resin cement has been put into practical use.
- Similar to the resin cement described later there are problems that the time in a semi-cured state is short and the timing of removal is difficult, and that when it is completely cured, the mechanical strength is too high and the removal is extremely difficult.
- resin cements are composed of a composition containing a radical polymerizable monomer, an inorganic or organic filler, and a chemical polymerization initiator, and are cured by radical polymerization.
- gear and various metals is shown by mix
- a resin cement mainly containing an inorganic filler as a filler is superior in mechanical strength and durability.
- the cement contains a chemical polymerization initiator in an amount capable of completely curing the cement. Therefore, there is a problem that the semi-cured state is short and the removal timing is difficult.
- the resin cement boasting high adhesive strength with respect to dental materials and restoration materials for crowns, the surplus cement attached to areas other than the target part is completely cured and firmly bonded. If it does, the removal will become very difficult.
- Patent Document 1 discloses a technique for adding a polymerization inhibitor to delay the curing time
- Patent Document 2 incorporates a styrene derivative having a specific structure to reduce the operation time from the start of curing to the end of curing.
- a technique for increasing the length and improving the removal of excess cement in chemical hardening is disclosed.
- dental cements mainly composed of radically polymerizable monomers such as resin cements contain a photopolymerization initiator in addition to a chemical polymerization initiator, and have both photocurability and chemical curability.
- a dual-cure type material is widely used (Patent Document 3). JP-A-9-67222 Republished WO2003 / 057180 JP-T-2004-529946
- An object of the present invention is to provide a dental cement which is excellent in mechanical strength and removability of excess cement.
- the present inventors have determined the amount of photopolymerization initiator and the chemical polymerization initiator.
- the content of each is in a specific range, it is found that a composition having excellent removability of excess cement after light irradiation and at the same time excellent mechanical strength required as dental cement can be obtained.
- the invention has been completed.
- the present invention [1] It consists of a first agent and a second agent, both of the first agent and the second agent contain a polymerizable monomer (a) and a filler (b), and the first agent and / or
- the second agent further contains a photopolymerization initiator (c), and one of the first agent and the second agent is used as a chemical polymerization initiator (d) as an oxidizing agent (f) and a reducing agent ( a dental cement comprising an oxidizing agent (f) of a redox polymerization initiator comprising g) and the other containing a reducing agent (g),
- the photopolymerization initiator (c) contains an ⁇ -diketone, and the total content of the photopolymerization initiator (c) is 0.010 with respect to 100 parts by weight of the total amount of the polymerizable monomers (a).
- the polymerization accelerator (e) is 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzophenone, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite
- the dental cement of the present invention achieves both the removability when removing excess cement in a semi-cured state by light irradiation and the mechanical properties required for dental cement.
- the dental cement of the present invention is a dental cement containing a polymerizable monomer (a), a filler (b), a photopolymerization initiator (c) and a chemical polymerization initiator (d).
- a polymerizable monomer a
- filler b
- photopolymerization initiator c
- chemical polymerization initiator d
- It consists of the first agent and the second agent, Both the first agent and the second agent contain a polymerizable monomer (a) and a filler (b), and the first agent and / or the second agent contains a photopolymerization initiator (c).
- one of the first agent and the second agent is the redox polymerization initiator oxidizing agent (f) comprising the oxidizing agent (f) and the reducing agent (g) as the chemical polymerization initiator (d), and the other is the reducing agent.
- the total content of the photopolymerization initiator (c) is 0.010 to 0.100 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomers (a)
- the chemical polymerization initiator (d) is characterized in that the total content is 0.001 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a).
- “content” means “content” and / or “blending amount”.
- Conventional dental cement contains 0.2 to 1 part by weight of a photopolymerization initiator with respect to 100 parts by weight of the total amount of polymerizable monomers.
- the total content of the photopolymerization initiator is 0.010 to 0.100 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomers, which is lower than the conventional product, and at the same time, the chemical polymerization initiator.
- the dental cement of the present invention comprises a first agent and a second agent, and contains a polymerizable monomer (a), a filler (b), a photopolymerization initiator (c), and a chemical polymerization initiator (d).
- the polymerizable monomer (a) is necessary as a component of the paste-like dental cement, and since the polymerization reaction proceeds with the polymerization initiator to become a polymer, it is used as either the first agent or the second agent. Is also contained.
- a radical polymerizable monomer having a polymerizable group is preferable. From the viewpoint of easy radical polymerization, the polymerizable group is a (meth) acryl group and / or (meth) acrylamide. Groups are preferred.
- the dental cement of the present invention is used in the oral cavity, the oral cavity is a moist environment and there is a possibility that the polymerizable group may be detached due to hydrolysis or the like.
- the polymerizable group is preferably a methacryl group and / or a methacrylamide group.
- (meth) acryl means acryl and methacryl
- (meth) acryloyl means acryloyl and methacryloyl.
- examples of the polymerizable monomer (a) include a polyfunctional monomer having a plurality of the following polymerizable groups and a monofunctional monomer having one of the following polymerizable groups.
- polyfunctional monomer examples include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, and trifunctional or higher functional polymerizable monomers. It is done.
- 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) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) ) Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyv Nyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl)
- 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane and 2,2-bis ( 4- (Meth) acryloyloxypolyethoxyphenyl) propane is preferred.
- 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane a compound having an average addition mole number of ethoxy groups of 2.6 (common name “D2.6E”) is preferable.
- aliphatic compound-based bifunctional polymerizable monomers examples include glycerol 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-pentanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2, , 4-trimethylhexamethylene bis (2-carbamoyloxyethyl)
- glycerol di (meth) acrylate triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2,4-trimethylhexa is preferable in terms of excellent handleability of the resulting dental cement.
- Methylene bis (2-carbamoyloxyethyl) dimethacrylate and 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane are preferred.
- trifunctional or higher polymerizable monomers examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like.
- N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra has a high mechanical strength in the resulting dental cement.
- Methacrylate is preferred.
- monofunctional monomers examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Decyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- ( Dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Acrylate), benzyl (meth) acrylate, lauryl (meth) acryl
- 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and glycerol mono (meth) acrylate are high in affinity with the dental cement of the resulting dental cement and have high adhesive strength.
- erythritol mono (meth) acrylate is preferred.
- the dental cement of the present invention may contain an acidic group-containing polymerizable monomer as the polymerizable monomer (a) from the viewpoint of good adhesion strength to the tooth and the dental prosthesis.
- an acidic group-containing polymerizable monomer 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 is polymerized.
- radically polymerizable monomers having a functional group is
- Examples of the polymerizable monomer having a phosphoric acid group include, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxy.
- polymerizable monomers having a pyrophosphate group include, for example, bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], bis [6 (6) pyrophosphate -(Meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and ammonium salts thereof Etc. are exemplified.
- Examples of the polymerizable monomer having a thiophosphate group include, for example, 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- (meth) Acryloyloxybutyl dihydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl diphosphate Idrogen thiophosphate, 11- (meth) acryloyloxyundecy
- polymerizable monomers having a phosphonic acid group examples include, for example, 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) Acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyl Examples thereof include oxydecyl-3-phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.
- Examples of the polymerizable monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylate and the like.
- Examples of the polymerizable monomer having a carboxylic acid group 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, N- (meth) acryloyl-5-amino.
- Salicylic acid O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid Acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and acid halides thereof It is exemplified.
- Examples of polymerizable monomers having a plurality of carboxyl groups in the molecule include 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, and 2- (meth) acryloyloxyethyl.
- the acidic group-containing polymerizable monomer preferably has a phosphoric acid group or a phosphonic acid group from the viewpoint of good adhesive strength of dental cement. It is more preferable to have a group.
- the alkyl group or alkylene group having 6 to 20 carbon atoms in the main chain is preferable in the molecule, and the main chain has 8 carbon atoms in the molecule such as 10- (meth) acryloyloxydecyl dihydrogen phosphate. More preferably, it has ⁇ 12 alkylene groups.
- the polymerizable monomer (a) may be used alone, but from the viewpoint of mechanical strength, handleability, adhesive strength and curability of dental cement, aromatic compound-based bifunctional polymerization. It is preferable to use the functional monomer in combination with an aliphatic compound-based bifunctional polymerizable monomer and / or a monofunctional monomer.
- the ratio in the case of using them together is not particularly limited, but when the total amount of the polymerizable monomer (a) is 100 parts by weight, the blending amount of the aromatic compound-based bifunctional polymerizable monomer is 40. Is preferably 90 parts by weight, more preferably 50 to 80 parts by weight, and still more preferably 55 to 75 parts by weight.
- the amount of the acidic group-containing polymerizable monomer is not particularly limited, but is preferably 1 to 60 parts by weight when the total amount of the polymerizable monomer (a) is 100 parts by weight.
- the amount is more preferably 50 parts by weight, and further preferably 5 to 40 parts by weight.
- the blending amount of the acidic group-containing polymerizable monomer is 1 part by weight or more, good adhesive strength is obtained, and when the blending amount of the acidic group-containing polymerizable monomer is 60 parts by weight or less, The polymerizability of the dental cement is moderate and the adhesive strength is also kept good.
- the filler (b) is necessary for adjusting the paste properties of the dental cement before curing and for increasing the mechanical strength after curing, and is contained in both the first agent and the second agent.
- examples of such fillers include organic fillers, inorganic fillers, and organic-inorganic composite fillers.
- Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene.
- Examples thereof include rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc., either alone or as a mixture of two or more. Can be used.
- the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.
- Inorganic fillers include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, alumino Examples thereof include silicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. These can also be used individually or in mixture of 2 or more types.
- the shape of the inorganic filler is not particularly limited, and an amorphous filler and a spherical filler can be appropriately selected and used.
- the inorganic filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent as necessary.
- a known surface treatment agent such as a silane coupling agent
- surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like.
- a known method can be used without any particular limitation.
- heating is usually performed in the range of 50 to 150 ° C. to complete the reaction between the surface of the inorganic filler and the surface treatment agent. It can be carried out.
- the organic-inorganic composite filler is obtained by previously adding a polymerizable monomer to the above-mentioned inorganic filler, forming a paste, polymerizing, and pulverizing.
- a polymerizable monomer for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used.
- the shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.
- the average particle size of the filler (b) is preferably from 0.001 to 50 ⁇ m, more preferably from 0.001 to 10 ⁇ m, from the viewpoints of the handleability and mechanical strength of the resulting dental cement.
- the average particle size of the filler can be measured by any method known to those skilled in the art, and can be easily measured by, for example, a laser diffraction type particle size distribution measuring apparatus described in the following examples.
- the blending amount of the filler (b) is not particularly limited, but from the viewpoint of handleability and mechanical strength of the resulting dental cement, 100 to 900 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). Preferably, the amount is 130 to 600 parts by weight, more preferably 150 to 400 parts by weight. If the content of the filler (b) is 100 parts by weight or more, the mechanical strength of the cured product is good, and if it is 900 parts by weight or less, the fluidity of the dental cement becomes appropriate and sufficient mixing is achieved. This can be done, and there is no fear that the strength of the cured product will decrease.
- the photopolymerization initiator (c) is necessary for the dental cement to start polymerization by light irradiation, and is contained in the first agent and / or the second agent.
- the use of ⁇ -diketones as these photopolymerization initiators has one feature.
- ⁇ -diketones By using ⁇ -diketones, it has excellent photocurability in the visible and near-ultraviolet region, and has sufficient photocurability using any light source such as a halogen lamp, light emitting diode (LED), or xenon lamp. Cement is obtained.
- any light source such as a halogen lamp, light emitting diode (LED), or xenon lamp. Cement is obtained.
- ⁇ -diketones examples include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. Can be mentioned. Among these, camphorquinone is preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.
- (bis) acylphosphine oxides and salts thereof, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, and coumarins to the extent that the effects of the present invention are not impaired.
- Anthraquinones, benzoin alkyl ethers, ⁇ -amino ketones and other photopolymerization initiators hereinafter also referred to as photopolymerization initiators other than ⁇ -diketones
- photopolymerization initiators other than ⁇ -diketones may be used in combination with ⁇ -diketones.
- the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 , 4,6-Trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) Examples thereof include phosphonates.
- bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- (2,6-dichloro).
- Benzoyl) -4-propylphenylphosphine oxide bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, ( 2 Such as 5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.
- a salt of (bis) acyl phosphine oxides A well-known salt is mentioned.
- the water-soluble acylphosphine oxides preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion or ammonium ion in the acylphosphine oxide molecule.
- water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.
- water-soluble acylphosphine oxides include monomethylacetylphosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethylbenzoylphosphonate / sodium, monomethyl (1-oxobutyl) phosphonate / sodium, Monomethyl (2-methyl-1-oxopropyl) phosphonate sodium, acetyl phosphonate sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxymethoxyphosphinyl) -4 -Oxobutanoate sodium salt, methyl-4-oxo-phosphonobutanoate mononatrium salt, acetylphenylphosphinate sodium salt, (1- Xoxopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylphen
- acylphosphine oxides and water-soluble acylphosphine oxides 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6 -Trimethylbenzoyl) acylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.
- thioxanthones or quaternary ammonium salts of thioxanthones include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H-thioxanthen-4-yloxy)- N, N, N-trimethyl-propaneaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propaneaminium chloride 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9- Oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N
- the preferred thioxanthone is 2-chlorothioxanthen-9-one
- the preferred quaternary ammonium salt of thioxanthones is 2-hydroxy -3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.
- ketals examples include benzyl dimethyl ketal and benzyl diethyl ketal.
- Examples of the coumarin compound include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitro Benzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7- Dimethylaminocoumarin, 3-benzoylbenzo [f] coumarin, 3-cal Xycoumarin, 3-carboxy-7-methoxycoumarin, 3-eth
- anthraquinones examples include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-hydroxyanthraquinone and the like.
- benzoin alkyl ethers examples include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
- ⁇ -aminoketones examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
- the content of ⁇ -diketone in the photopolymerization initiator (c) is preferably 50% by weight or more, more preferably 60% by weight or more, and more preferably 65 to 100% by weight from the viewpoint of photocurability of the dental cement to be obtained. Is more preferable.
- the content of the photopolymerization initiator (c) other than the ⁇ -diketone in the photopolymerization initiator (c) is preferably 50% by weight or less from the viewpoint of achieving both photocurability and aesthetics of the resulting dental cement. It is more preferably 40% by weight or less, and further preferably 0 to 35% by weight.
- the total amount of the photopolymerization initiator (c) is 0.010 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a) in that the obtained dental cement is excellent in removing excess cement. 0.100 parts by weight, preferably 0.010 to 0.095 parts by weight, more preferably 0.010 to 0.090 parts by weight, and 0.020 to 0.080 parts by weight. More preferred is 0.030 to 0.080 parts by weight.
- the total amount of the photopolymerization initiator (c) is 0.010 part by weight or more, it is possible to maintain the mechanical strength and adhesive strength of the cured product favorably, and 0.100 part by weight or less. When it is, the hardening of the surplus cement immediately after hardening by light irradiation will become moderate, and the removability of the surplus cement will be excellent.
- the dental cement of the present invention contains a chemical polymerization initiator (d) in addition to the photopolymerization initiator (c).
- a chemical polymerization initiator (d) By including a chemical polymerization initiator (d), it becomes possible to polymerize a portion where light does not reach when using a light-impermeable crown restorative material, and also to initiate polymerization after removing excess cement. Therefore, the polymerization hardening of dental cement can be promoted and the mechanical strength after removing the excess cement can be further increased.
- a chemical polymerization initiator (d) a redox polymerization initiator composed of an oxidizing agent (f) and a reducing agent (g) is used, and the oxidizing agent (f) is used as either the first agent or the second agent.
- the reducing agent (g) is contained in the other.
- Examples of the oxidizing agent (f) of the redox polymerization initiator include organic peroxides, azo compounds, and inorganic peroxides.
- Examples of the organic peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides.
- Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, and the like.
- peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy Examples include -2-ethylhexanoate and t-butyl peroxyisopropyl carbonate.
- dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like.
- peroxyketals include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis And (t-hexylperoxy) cyclohexane.
- ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide.
- hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like.
- azo compound examples include azobisisobutyronitrile and azobisisobutylvaleronitrile.
- inorganic peroxides include sodium persulfate, potassium persulfate, aluminum persulfate, and ammonium persulfate.
- Examples of the reducing agent (g) for the redox polymerization initiator include aromatic amines, thioureas, and ascorbic acid that do not have an electron withdrawing group in the aromatic ring.
- Specific examples of the aromatic amine having no electron withdrawing group in the aromatic ring include 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 -B
- the aromatic amine which does not have an electron withdrawing group in the aromatic ring mentioned above one kind may be used alone or plural kinds may be used in combination.
- Thioureas include thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea.
- Triethylthiourea tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like. Any of the above-described thiourea compounds may be used alone or in combination.
- the total blending amount of the chemical polymerization initiator (d) [total blending amount of the oxidizing agent (f) and the reducing agent (g)] is a polymerizable monomer from the viewpoint of curability of the dental cement to be obtained. It is 0.001 to 20 parts by weight with respect to 100 parts by weight of the total amount of (a).
- the compounding amount of the chemical polymerization initiator (d) if the total compounding amount of the oxidizing agent and the reducing agent is 0.001 part by weight or more, both the mechanical strength and the adhesive strength of the cured product can be achieved. It is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more.
- the adhesive strength does not decrease, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less.
- the total amount of the chemical polymerization initiator (d) is 0.001 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a), and 0.01 to 10 parts by weight.
- 0.1 to 5 is more preferable.
- the ratio of the weight of the polymerization initiator (c) to the total weight of the chemical polymerization initiator (d) [photopolymerization initiator (c) / chemical polymerization initiator (d)] is preferably 1/28 to 1/5, More preferably, it is 1/27 to 1/10, more preferably 1/27 to 1/12, still more preferably 1/25 to 1/20.
- the photopolymerization initiator (c) and the chemical polymerization initiator (d) are used together with a polymerization accelerator (e).
- a polymerization accelerator (e) used in the present invention include aliphatic amines, aromatic tertiary amines having an electron-withdrawing group, sulfinic acid and its salts, sulfur-containing reducing inorganic compounds, borate compounds, barbi compounds.
- Examples include tool acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, and thiol compounds.
- aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methyldiethanolamine; N-methyl Diethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) acrylate , Triethanolamine mono (meth) acrylate, triethanolamine di (meth) acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine Tertiary aliphatic amines such as tributylamine and the like. Among these, tert
- the hydrogen atom of the aromatic ring of the aromatic tertiary amine is an electron withdrawing group such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group.
- an electron withdrawing group such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group.
- Specific examples include 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, 4-N, N-dimethylaminobenzoic acid.
- Acid propyl ester 4-N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2-[(meth) acryloyloxy] ethyl ester, 4-N, N-dimethylamino Examples include benzophenone.
- 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxy Ethyl ester, 4-N, N-dimethylaminobenzophenone is preferred.
- sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and benzenesulfin.
- Reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. Specific examples include sodium sulfite, potassium sulfite , Calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.
- the borate compound is preferably an aryl borate compound.
- aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule.
- borate compound having two aryl groups in one molecule examples include dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl.
- dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and Alkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group and the like) and salts thereof
- borate compounds having three aryl groups in one molecule include monoalkyltriphenyl boron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri ( p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoa Kirtri (p-o
- borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenyl boron.
- Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid Acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbi Tool acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, -Benzy
- triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-tria
- copper compound for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are suitably used.
- tin compound examples include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate.
- preferred tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.
- the vanadium compounds are preferably IV and / or V vanadium compounds.
- IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003-1990 (Phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V), etc. And compounds described in Japanese Patent No. -96122.
- halogen compound for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used.
- aldehydes include terephthalaldehyde and benzaldehyde derivatives.
- benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.
- thiol compound examples include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.
- the blending amount of the polymerization accelerator (e) is not particularly limited, but from the viewpoint of curability and the like of the resulting composition, 0.001 to 20% by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). It is preferable to contain a part.
- the blending amount of the polymerization accelerator (e) is 0.001 part by weight or more, the mechanical strength and adhesive strength of the cured product become favorable, more preferably 0.01 part by weight or more, and further preferably 0.1 parts by weight or more.
- the blending amount of the polymerization accelerator (e) is 20 parts by weight or less, the adhesive strength is not lowered, the color tone of the composition is not deteriorated, and the discoloration of the cured product can be prevented. Is 15 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less.
- a publicly known additive can be mix
- additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners, and the like.
- the dental cement of the present invention is not particularly limited as long as it contains the polymerizable monomer (a), filler (b), photopolymerization initiator (c) and chemical polymerization initiator (d). Resin cement and resin reinforced glass ionomer cement can be easily produced by methods known to those skilled in the art.
- the chemical polymerization initiator (d) is a redox polymerization initiator comprising an oxidizing agent (f) and a reducing agent (g), the oxidizing agent (f) and the reducing agent (g ) In a separate container. That is, in the embodiment, the dental cement of the present invention is provided as a kit used in a two-part form, and in a more preferred embodiment, it is provided as a kit used in a two-paste form. When used in the form of a two-paste type, it is preferable to store each paste in a state where the pastes are separated from each other, knead the two pastes immediately before use, and proceed with chemical polymerization and photopolymerization to cure.
- the dental cement of the present invention is used as a resin cement
- the dental cement is preferably a composition containing (a), (b), (c), (d) and (e).
- a paste and B paste are both the polymerizable monomer (a) and the filler (b).
- at least one of them contains the photopolymerization initiator (c)
- one of them contains the oxidizing agent (f) of the chemical polymerization initiator (d)
- the other contains the reducing agent (g)
- a polymerization accelerator (e) it is preferable that either one contains a polymerization accelerator (e).
- the polymerizable monomer (a) contains an acidic group-containing polymerizable monomer
- the acidic group-containing polymerizable monomer is preferably contained in one of the A and B pastes. .
- the dental cement of the present invention When used as a resin-reinforced glass ionomer cement, the dental cement typically comprises an inorganic filler such as fluoroaluminosilicate glass, a polyalkenoic acid such as polyacrylic acid, and water. It is desirable to have a composition that contains and has a mechanism of reacting and curing by an acid-base reaction. Specifically, (a), (b), (c), (d), (e) A composition containing polyalkenoic acid and water is preferred. In this mechanism, it is considered that the adhesion function is expressed by the interaction between the polyalkenoic acid and calcium in the hydroxyapatite constituting the tooth substance.
- Polyalkenoic acid is a polymer of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
- Specific examples of the polyalkenoic acid include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, Examples thereof include homopolymers such as uraconic acid, and copolymers with monomers that are copolymerizable with these unsaturated carboxylic acids.
- the proportion of unsaturated carboxylic acid units is preferably 50 mol% or more based on the total structural units.
- the copolymerizable monomer is preferably an ethylenically unsaturated polymerizable monomer such as styrene, acrylamide, acrylonitrile, methyl methacrylate, acrylates, vinyl chloride, allyl chloride, vinyl acetate, 1,1,6. -Trimethylhexamethylene dimethacrylate ester and the like.
- polyalkenoic acids homopolymers or copolymers of acrylic acid or maleic acid are preferred. When these polyalkenoic acids have a weight average molecular weight of less than 5,000, the strength of the cured product of the dental cement composition is lowered, and the durability may be inferior.
- the preferred polyalkenoic acid has a weight average molecular weight of 5,000 to 40,000.
- the blending amount of these polyalkenoic acids is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). It is more preferable to include a part.
- the filler (b) used when the dental cement of the present invention is used as a resin-reinforced glass ionomer cement
- the above-mentioned inorganic filler is used.
- the amount of water used when the dental cement of the present invention is used as a resin-reinforced glass ionomer cement includes 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). It is preferably 10 to 300 parts by weight, more preferably 20 to 100 parts by weight. By containing water in such a range, the acid-base reaction can proceed smoothly, and the obtained cured product has good mechanical strength and adhesion to the tooth.
- the A paste contains the polymerizable monomer (a), the filler (b), polyalkenoic acid and water.
- the B paste contains the polymerizable monomer (a) and the filler (b), and at least one contains the photopolymerization initiator (c), and either one contains the chemical polymerization initiator.
- the A paste contains the polymerizable monomer (a), the filler (b) and polyalkenoic acid
- the B paste contains the polymerizable monomer (a), the filler (b) and water.
- at least one contains the photopolymerization initiator (c), and one of the chemical polymerization initiator (d) is an oxidizing agent (f) and the other is a reducing agent (g).
- each contains a polymerization accelerator (e).
- the filler (b) contained in the B paste includes fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and barium fluoro. It is preferable to use at least one selected from the group consisting of aluminosilicate glass and strontium calcium fluoroaluminosilicate glass, and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass.
- the filler (b) contained in the A paste it is preferable to use a filler that does not react with polyalkenoic acid, and quartz is preferably used.
- the dental cement of the present invention thus obtained has a compressive elastic modulus of 100 to 400 MPa immediately after photocuring.
- the compressive elastic modulus is an index representing hardness, and is a value indicating how much force should be applied per unit area to compress a certain substance to zero thickness. The larger this value is, the harder the material is.
- the compressive elastic modulus immediately after light irradiation is 100 to 400 MPa, preferably 150 to 370 MPa, more preferably 200 to 350 MPa. More preferably, it is 250 to 350 MPa.
- the compressive elastic modulus immediately after light irradiation is 100 MPa or more, the mechanical strength is obtained so that it can be removed as a lump in the surplus cement after curing, and the removability is excellent.
- the compression modulus immediately after the light irradiation is 400 MPa or less, the mechanical strength of the dental cement immediately after the light irradiation does not become too high, and it does not adhere firmly to the tooth or the dental restorative material. Easy to remove cement.
- the compressive elasticity modulus of dental cement is measured by the method as described in the below-mentioned Example.
- the dental cement of the present invention has a compressive elastic modulus of 500 MPa or more after 24 hours from light irradiation.
- the compressive elastic modulus 24 hours after light irradiation is preferably 600 to 1500 MPa, more preferably 750 to 1500 MPa, The pressure is preferably 900 to 1500 MPa.
- the compressive elastic modulus 24 hours after light irradiation is 500 MPa or more, the distortion to pressure such as occlusal pressure does not become too large, and even if applied for a long time in the oral cavity, dental cement There is no risk of collapse or loss of dental restorative materials.
- the dental paste A paste and B paste of the present invention are mixed just before use to make one paste, and then a slightly excessive amount of dental cement is applied to the inner wall surface of the restoration material for the crown before the curing starts. , Press the teeth. During this pressure welding operation, excess dental cement is allowed to protrude from the joint (margin) between the tooth and the crown restorative material, and the excess cement is temporarily irradiated using a dental light irradiator. To make the excess cement semi-cured.
- the light irradiation time for making the semi-cured state varies depending on the type and light quantity of the light irradiator, but is usually about 2 to 5 seconds.
- the surplus cement is removed by using a dental short needle or the like for the surplus cement thus semi-cured.
- the tooth surface Prior to applying the dental cement of the present invention to the tooth surface, the tooth surface is conventionally treated with an etching solution with an acidic aqueous solution, a modification treatment with a primer, a simultaneous etching / modification treatment with a primer having etching ability, etc.
- a known pretreatment may be performed.
- these surface treatment agents known ones can be used without any limitation.
- the inorganic fillers 1 and 2 are obtained according to the following production method.
- Inorganic filler 1 Silane-treated barium glass powder
- Barium glass manufactured by STEC, product code “Raysorb E-3000” was pulverized with a ball mill to obtain barium glass powder.
- the average particle diameter of the obtained barium glass powder was measured by using a laser diffraction particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, model “SALD-2100”) and found to be 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.
- Inorganic filler 2 Silane-treated colloidal silica powder In 100 parts by weight of distilled water, 0.3 parts by weight of acetic acid and 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane are added and stirred, and further colloidal silica powder (Nippon Aerosil Co., Ltd.) Product code “Aerosil OX50”) was added and stirred for 1 hour. After removing water by freeze-drying, heat treatment was performed at 80 ° C. for 5 hours to obtain a silane-treated colloidal silica powder.
- Examples 1 to 12 and Comparative Examples 1 to 3 Preparation of dual cure type resin cement
- Table 1 or 2 The raw materials shown in Table 1 or 2 were mixed at room temperature to prepare A paste and B paste, and the characteristics were examined according to the methods of Test Examples 1 to 3 below. The results are shown in Tables 1 and 2.
- Test Example 1 Compressive modulus immediately after light irradiation
- a paste and B paste collected in equal amounts were mixed with a dental kneading rod for 10 seconds, and then immediately filled into a stainless steel mold having a hole with a diameter of 4 mm and a height of 4 mm.
- the upper and lower surfaces of the mold are pressure-contacted with a release film (polyester), and an irradiation device “JET Light 3000” (manufactured by J. Morita USA) is applied to dental cement from the upper surface 1 minute after the start of mixing through the release film. Was used for 20 seconds.
- the stainless steel mold was turned upside down, and the opposite surface was irradiated with light for 20 seconds, and then removed from the mold to obtain one hardened body of dental cement. Further, three hardened bodies were prepared in the same manner, and a total of four dental cement hardened bodies were obtained.
- One hardened body of the obtained dental cement was compressed at a crosshead speed of 1 mm / min using a compression tester (Autograph, manufactured by Shimadzu Corporation) 3 minutes after the start of mixing of the dental cement.
- the compression modulus of the cured product was measured by a least square method between 50N and 100N.
- the compression elastic modulus was measured 3 minutes after the start of mixing of the dental cement, and the average value of the four compression elastic moduli was used as the value of the compression elastic modulus immediately after light irradiation. did.
- Test Example 2 compression modulus after 24 hours
- a cured body of dental cement was prepared in the same manner as in Test Example 1, and the resulting cured body was immersed in water at 37 ° C. for 24 hours, and then the compression modulus was measured in the same manner as in Test Example 1. Similarly, the compression modulus was measured for the remaining three cured bodies, and the average value of the four compression modulus was taken as the value of the compression modulus after 24 hours.
- Test Example 3 (Removability of excess cement) The lip surface of bovine mandibular anterior teeth was polished with silicon carbide paper under running water to expose the flat surface of dentin. The exposed flat surface was further polished with # 1000 silicon carbide paper under running water, and then the surface water was dried by air blowing.
- the resin cements of the examples have both mechanical strength and excess cement removability compared to the resin cements of the comparative examples.
- the content of the chemical polymerization initiator (d) is the same as in Example 1, but the content of the photopolymerization initiator (c) is 0 with respect to 100 parts by weight of the total amount of the polymerizable monomers (a).
- the content of the photopolymerization initiator (c) is the same as that of Example 9 in which Example 9 is 0.025 part by weight, but the content of the chemical polymerization initiator (d) is the same as that of the polymerizable monomer (a).
- Example 8 which is 3.2 parts by weight with respect to 100 parts by weight as a whole maintains moderate mechanical strength and excess cement removability, although the removability of surplus cement is slightly inferior.
- Examples 1 to 5 and Example 10 in which the ratio of the total weight of the photopolymerization initiator to the total weight of the chemical polymerization initiator is in a specific range and the total amount of the photopolymerization initiator is in a specific range. Then, the removability of excess cement and appropriate mechanical strength are compatible at a higher level, and the contents of the photopolymerization initiator (c) and the chemical polymerization initiator (d) are within a specific range. It is suggested that it is important.
- the dental cement of the present invention is suitably used in the field of dentistry, for example, when bonding a dentine and a restoration for a crown.
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Abstract
Description
〔1〕 第1剤と第2剤からなり、前記第1剤及び第2剤のいずれもが重合性単量体(a)及びフィラー(b)を含有し、かつ前記第1剤及び/又は前記第2剤が光重合開始剤(c)をさらに含有してなり、さらに前記第1剤及び第2剤のいずれか一方が化学重合開始剤(d)として酸化剤(f)及び還元剤(g)からなるレドックス重合開始剤の酸化剤(f)を、他方が還元剤(g)をそれぞれ含有してなる歯科用セメントであって、
前記光重合開始剤(c)がα-ジケトン類を含有し、前記光重合開始剤(c)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.010~0.100重量部、前記化学重合開始剤(d)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.001~20重量部であり、光硬化させた直後の硬化物の圧縮弾性率が100~400MPa、24時間後の該圧縮弾性率が500MPa以上である、歯科用セメント、
〔2〕 重合性単量体(a)が重合性基として(メタ)アクリル基及び/又は(メタ)アクリルアミド基を有する重合性単量体である前記〔1〕記載の歯科用セメント、
〔3〕 光重合開始剤(c)の総重量と化学重合開始剤(d)の総重量の比〔光重合開始剤(c)/化学重合開始剤(d)〕が1/28~1/5である、前記〔1〕又は〔2〕記載の歯科用セメント、
〔4〕 さらに、重合促進剤(e)を重合性単量体(a)の総量100重量部に対して0.001~20重量部含有してなる、前記〔1〕~〔3〕いずれか記載の歯科用セメント、
〔5〕 重合促進剤(e)が4-N,N-ジメチルアミノ安息香酸エチルエステル、4-N,N-ジメチルアミノ安息香酸メチルエステル、N,N-ジメチルアミノ安息香酸n-ブトキシエチルエステル、4-N,N-ジメチルアミノベンゾフェノン、ベンゼンスルフィン酸ナトリウム、p-トルエンスルフィン酸ナトリウム、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、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸カルシウム、亜硫酸アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウムからなる群より選ばれる少なくとも1種である、前記〔4〕記載の歯科用セメント、ならびに
〔6〕 第1剤が第1のペースト(A)、第2剤が第2のペースト(B)である、前記〔1〕~〔5〕いずれか記載の歯科用セメント
に関する。
第1剤と第2剤からなり、
前記第1剤及び第2剤のいずれもが重合性単量体(a)及びフィラー(b)を含有し、かつ
前記第1剤及び/又は前記第2剤が光重合開始剤(c)をさらに含有し、
さらに前記第1剤及び第2剤のいずれか一方が化学重合開始剤(d)として酸化剤(f)及び還元剤(g)からなるレドックス重合開始剤の酸化剤(f)を、他方が還元剤(g)をそれぞれ含有するものである。
本発明においては、前記構成において、前記光重合開始剤(c)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.010~0.100重量部、前記化学重合開始剤(d)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.001~20重量部である点に大きな特徴を有する。なお、本明細書において、「含有量」とは、「含有量」及び/又は「配合量」を意味する。
D-2.6E: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
NPG:ネオペンチルグリコールジ(メタ)アクリレート
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
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
無機フィラー1及び2は、以下の製造方法に従って得られる。
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、バリウムガラス粉を得た。得られたバリウムガラス粉の平均粒子径をレーザー回折式粒度分布測定装置(島津製作所製、型式「SALD-2100」)を用いて測定したところ、2.4μmであった。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。
蒸留水100重量部中に0.3重量部の酢酸と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を加えて攪拌し、さらにコロイドシリカ粉末(日本アエロジル社製、商品コード「アエロジルOX50」)を50重量部加えて1時間攪拌した。凍結乾燥により水を除去した後、80℃で5時間加熱処理を行い、シラン処理コロイドシリカ粉末を得た。
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
BPO:ベンゾイルパーオキサイド
DEPT:N,N-ジ(2-ヒドロキシエチル)-p-トルイジン
DBB:N,N-ジメチルアミノ安息香酸n-ブトキシエチルエステル
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
BHT:2,6-ジ-t-ブチル-4-メチルフェノール
表1又は2に示す原料を常温下で混合してAペースト及びBペーストを調製し、以下の試験例1~3の方法に従って特性を調べた。結果を表1及び2に示す。
各実施例及び比較例について、等量採取したAペーストとBペーストを歯科用練和棒で10秒間混合した後、直ちに直径4mm、高さ4mmの孔を有するステンレス製の型に充填した。型の上下の面を離型フィルム(ポリエステル)で圧接し、前記離型フィルムを介して、混合開始から1分後に上面から歯科用セメントに照射器「JETライト3000」(J.Morita USA製)を用いて20秒間光照射を行った。続いてステンレス製の型の上下を逆さにして反対側の面にも20秒間光照射を行った後、型から取り出して歯科用セメントの硬化体を1個得た。さらに、同様にして3個の硬化体を調製し、合計4個の歯科用セメント硬化体を得た。
試験例1と同様にして歯科用セメントの硬化体を調製し、得られた硬化体を37℃の水中に24時間浸漬後、試験例1と同様にして圧縮弾性率を測定した。同様にして、残る3個の硬化体についても圧縮弾性率を測定し、4個の圧縮弾性率の平均値をもって24時間後の圧縮弾性率の値とした。
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、その後、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、各実施例及び比較例について、等量採取したAペーストとBペーストを10秒間混合することにより得られた、各実施例及び比較例の歯科用セメント0.5gを塗布し、その上から5mm×5mmのステンレス板を圧接した。圧接によりはみ出した余剰セメントに対して、試験例1と同様の歯科用照射器「JETライト3000」を用いて、ステンレス板の四面の各方向から5秒ずつ光照射を行った。その後、短針を用いて余剰レジンを除去し、以下の評価基準に従って、余剰セメントの除去性を評価した。
A:容易に一塊で余剰セメントを除去することが可能
B:余剰セメントは硬く歯質と接着しているが、一塊で除去することが可能
C:余剰セメントは脆いが、余剰セメントのみの除去は可能
D:余剰セメントが脆く、圧接部からの過剰除去あり
E:余剰セメントの強度が高く、歯質と強固に接着しているため除去が困難
Claims (6)
- 第1剤と第2剤からなり、前記第1剤及び第2剤のいずれもが重合性単量体(a)及びフィラー(b)を含有し、かつ前記第1剤及び/又は前記第2剤が光重合開始剤(c)をさらに含有してなり、さらに前記第1剤及び第2剤のいずれか一方が化学重合開始剤(d)として酸化剤(f)及び還元剤(g)からなるレドックス重合開始剤の酸化剤(f)を、他方が還元剤(g)をそれぞれ含有してなる歯科用セメントであって、
前記光重合開始剤(c)がα-ジケトン類を含有し、前記光重合開始剤(c)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.010~0.100重量部、前記化学重合開始剤(d)の総含有量が前記重合性単量体(a)の総量100重量部に対して0.001~20重量部であり、光硬化させた直後の硬化物の圧縮弾性率が100~400MPa、24時間後の該圧縮弾性率が500MPa以上である、歯科用セメント。 - 重合性単量体(a)が重合性基として(メタ)アクリル基及び/又は(メタ)アクリルアミド基を有する重合性単量体である請求項1記載の歯科用セメント。
- 光重合開始剤(c)の総重量と化学重合開始剤(d)の総重量の比〔光重合開始剤(c)/化学重合開始剤(d)〕が1/28~1/5である、請求項1又は2記載の歯科用セメント。
- さらに、重合促進剤(e)を重合性単量体(a)の総量100重量部に対して0.001~20重量部含有してなる、請求項1~3いずれか記載の歯科用セメント。
- 重合促進剤(e)が4-N,N-ジメチルアミノ安息香酸エチルエステル、4-N,N-ジメチルアミノ安息香酸メチルエステル、N,N-ジメチルアミノ安息香酸n-ブトキシエチルエステル、4-N,N-ジメチルアミノベンゾフェノン、ベンゼンスルフィン酸ナトリウム、p-トルエンスルフィン酸ナトリウム、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、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸カルシウム、亜硫酸アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素カリウムからなる群より選ばれる少なくとも1種である、請求項4記載の歯科用セメント。
- 第1剤が第1のペースト(A)、第2剤が第2のペースト(B)である、請求項1~5いずれか記載の歯科用セメント。
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JP2009548064A JP5114498B2 (ja) | 2007-12-28 | 2008-12-25 | 歯科用セメント |
CA2709518A CA2709518A1 (en) | 2007-12-28 | 2008-12-25 | Cement for dental applications |
EP08866884.3A EP2226060B1 (en) | 2007-12-28 | 2008-12-25 | Cement for dental applications |
CN200880123336XA CN101909579B (zh) | 2007-12-28 | 2008-12-25 | 牙科用粘固剂 |
ES08866884T ES2784030T3 (es) | 2007-12-28 | 2008-12-25 | Cemento para aplicaciones dentales |
US12/810,081 US8552088B2 (en) | 2007-12-28 | 2008-12-25 | Cement for dental applications |
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CN101909579A (zh) | 2010-12-08 |
EP2226060A4 (en) | 2013-12-18 |
ES2784030T3 (es) | 2020-09-21 |
CN101909579B (zh) | 2013-11-20 |
CA2709518A1 (en) | 2009-07-09 |
EP2226060A1 (en) | 2010-09-08 |
US20100267856A1 (en) | 2010-10-21 |
JPWO2009084586A1 (ja) | 2011-05-19 |
US8552088B2 (en) | 2013-10-08 |
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JP5114498B2 (ja) | 2013-01-09 |
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