WO2013145621A1 - 1液型の歯科用接着剤 - Google Patents
1液型の歯科用接着剤 Download PDFInfo
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- WO2013145621A1 WO2013145621A1 PCT/JP2013/001809 JP2013001809W WO2013145621A1 WO 2013145621 A1 WO2013145621 A1 WO 2013145621A1 JP 2013001809 W JP2013001809 W JP 2013001809W WO 2013145621 A1 WO2013145621 A1 WO 2013145621A1
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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
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/61—Cationic, anionic or redox initiators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
- A61K6/75—Apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/78—Pigments
-
- 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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
-
- 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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/822—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising rare earth metal oxides
-
- 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
- A61K6/889—Polycarboxylate cements; Glass ionomer cements
Definitions
- the present invention relates to a one-pack type dental adhesive, and more specifically, to bond a dental hard tissue (dental material) and a dental restorative material such as a dental composite resin, a dental compomer, and a dental resin cement.
- the present invention relates to a one-pack type dental adhesive used in the present invention.
- filling restoration materials such as filling composite resins and filling compomers, and teeth such as metal alloys, porcelain and resin materials are usually used.
- a crown repair material is used.
- the filling restorative material and the crown restorative material themselves are not adhesive to the tooth. For this reason, conventionally, various adhesion systems using an adhesive have been used for adhesion between a tooth and a dental restorative material.
- the surface of the tooth is etched using an acid etching agent such as an aqueous phosphoric acid solution, and then a bonding agent, which is an adhesive, is applied to the tooth and dental.
- an acid etching agent such as an aqueous phosphoric acid solution
- a bonding agent which is an adhesive
- acid-etching type adhesion system that adheres to a repair material.
- this adhesive system is a bonding containing a crosslinkable monomer and a polymerization initiator without applying water washing after applying a self-etching primer containing acidic monomer, hydrophilic monomer and water on the surface of the tooth.
- a two-step adhesive system for applying an adhesive has been the mainstream, but recently, a one-step adhesive system using a one-pack type dental adhesive having both functions of a self-etching primer and a bonding agent has been widely used. .
- This type of one-part dental adhesive is generally composed of acidic groups such as carboxylic acid groups, phosphonic acid groups, thiophosphoric acid groups, and phosphoric acid groups, which are constituents of self-etching primers and / or bonding agents. It contains a contained monomer, a hydrophilic monomer containing a hydroxyl group, a crosslinkable monomer, water, and a polymerization initiator.
- the monomer having a hydrophilic group includes an acidic group-containing monomer and a hydrophilic monomer.
- an acidic group-containing (meth) acrylate compound and a water-soluble (meth) acrylate compound containing a hydroxyl group are used. It was general.
- a monomer having a hydrophilic group a one-pack type dental adhesive using an acidic group-containing (meth) acrylate compound and a (meth) acrylamide compound having an amide group has been proposed. It has been reported that the use of such a one-part dental adhesive improves storage stability and provides high adhesion to dentin and enamel.
- Patent Document 1 discloses a one-component type containing an acidic group-containing polymerizable monomer, a water-soluble (meth) acrylamide compound, water, a curing agent, and a crosslinkable polymerizable monomer.
- Dental adhesives have been proposed.
- monofunctional (meth) acrylamide compounds are exemplified as the water-soluble (meth) acrylamide compounds.
- the one-component dental adhesive described in Patent Document 1 has room for improvement in adhesion to dentin, and the monofunctional (meth) acrylamide to be used. It has been found that there is a problem that storage stability may not be sufficient depending on the type of compound.
- Patent Document 2 discloses a one-part dental type containing a polymerizable acidic phosphate ester monomer having a specific structure, a polymerizable acidic monomer having a specific structure, a polymerizable N-substituted alkylacrylic acid amide monomer, an acrylic acid amide monomer, or the like.
- An adhesive has been proposed, and it is described that a monofunctional (meth) acrylamide compound or a polyfunctional (meth) acrylamide compound may be added to the adhesive.
- Patent Document 3 discloses at least one acid (meth) acrylamide monomer having two or more polymerizable groups, an acidic group-containing monomer, a polymerization initiator, and a monofunctional or polyfunctional non-acid (meth) acrylamide. Adhesives containing monomers have been proposed. However, according to the study by the present inventors, it has been found that the adhesives described in Patent Documents 2 and 3 may have poor adhesion to dentin and / or enamel depending on the composition. It was. Moreover, it turned out that the adhesive agent of patent document 2 and 3 has the problem that stability with respect to environmental light is low, and operation margin time is short.
- An object of the present invention is to provide a one-pack type dental adhesive exhibiting excellent adhesion to both enamel and dentin, and having high storage stability and environmental light stability.
- the present invention relates to a monofunctional (meth) acrylate compound (a) containing 1 to 30% by weight of a phosphate group, 10 to 50% by weight of a water-soluble polymerizable monomer (b), 5 to 50% by weight of hydrophobic crosslinkable (meth) acrylate compound (c), Containing water (d), and a polymerization initiator (e),
- the water-soluble polymerizable monomer (b) is a monofunctional (meth) acrylamide compound (b-1) represented by the following general formula (1) and a water-soluble crosslinkable (meth) acrylic monomer (B-2) in which the weight ratio of the monofunctional (meth) acrylamide compound (b-1) to the water-soluble crosslinkable (meth) acrylic monomer (b-2) is 10: 1.
- ⁇ 1 5, It is a one-pack type dental adhesive.
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group.
- the amount of water (d) is preferably 1 to 50% by weight, and the amount of polymerization initiator (e) is preferably 0.01 to 10% by weight.
- the water-soluble crosslinkable (meth) acrylic monomer (b-2) is a water-soluble bis (meth) acrylamide compound represented by the following general formula (2) and 1,2-bis (3-methacryloyl) It is preferably at least one selected from the group consisting of (oxy-2-hydroxypropyloxy) ethane.
- X is a linear or branched aliphatic group having 1 to 6 carbon atoms, and the group includes —O—, —S—, —CO—O—, —CO—NH—, — At least one bond selected from the group consisting of O—CO—NH— and —NH—CO—NH— may be inserted, and R 4 and R 5 each independently represents a hydrogen atom or a carbon number 1 to 4 linear or branched aliphatic groups, R 6 and R 7 are each independently a hydrogen atom or a methyl group.
- the monofunctional (meth) acrylamide compound (b-1) is preferably N, N-diethylacrylamide.
- a long one-part dental adhesive is provided.
- the one-component dental adhesive of the present invention comprises 1 to 30% by weight of a phosphate group-containing monofunctional (meth) acrylate compound (a), 10 to 50% by weight of a water-soluble polymerizable monomer (b ) 5 to 50% by weight of a hydrophobic crosslinkable (meth) acrylate compound (c), water (d), and a polymerization initiator (e).
- the water-soluble polymerizable monomer (b) includes a monofunctional (meth) acrylamide compound (b-1) represented by the general formula (1) and a water-soluble crosslinkable (meth) acrylic monomer.
- (B-2) in which the weight ratio of the monofunctional (meth) acrylamide compound (b-1) to the water-soluble crosslinkable (meth) acrylic monomer (b-2) is 10: 1. ⁇ 1: 5.
- (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to similar expressions.
- monomers with hydrophilic groups are important for chemical interaction with apatite in enamel and chemical interaction with collagen layer in dentin, which are important for obtaining high adhesion. Play an important role.
- a phosphate group-containing monofunctional (meth) acrylate compound (a) a specific monofunctional (meth)
- Three types of acrylamide compound (b-1) and water-soluble crosslinkable (meth) acrylic monomer (b-2) are blended in specific amounts, and a specific monofunctional (meth) acrylamide compound (b- 1) and water-soluble cross-linkable (meth) acrylic monomer (b-2) are used in a specific ratio, thereby providing high adhesion to both enamel and dentin, and higher It was found that storage stability was also obtained.
- the phosphate group-containing monofunctional (meth) acrylate compound (a) in the present invention penetrates and binds to the tooth while demineralizing the tooth. Since the (meth) acrylate compound (a) is monofunctional, higher adhesion to enamel can be obtained than a (meth) acrylate compound having a plurality of (meth) acryloyl groups. Moreover, since the acidic group of (meth) acrylate compound (a) is a phosphoric acid group, compared with the case where the (meth) acrylate compound which has other acidic groups, such as a phosphonic acid group, is used, it is high with respect to a tooth substance. Adhesiveness is obtained.
- Examples of phosphoric acid group-containing monofunctional (meth) acrylate compounds (a) include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxy Butyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) Acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acrylo
- a divalent phosphate group-containing monofunctional (meth) acrylate having an alkyl group or alkylene group having 6 to 20 carbon atoms as a main chain in the molecule A compound is preferable, and a divalent phosphate group-containing monofunctional (meth) acrylate compound having an alkylene group having 8 to 12 carbon atoms as a main chain in the molecule, such as 10-methacryloyloxydecyl dihydrogen phosphate, is more preferable.
- the phosphate group-containing monofunctional (meth) acrylate compound (a) may be used alone or in combination of two or more. Adhesive strength decreases when the amount of the phosphate group-containing monofunctional (meth) acrylate compound (a) is too large or too small.
- the amount of the phosphate group-containing monofunctional (meth) acrylate compound (a) is in the range of 1 to 30% by weight, preferably 3 to 20% by weight, based on the total weight of the dental adhesive.
- the water-soluble polymerizable monomer (b) is a monofunctional (meth) acrylamide compound (b-1) represented by the following general formula (1) and a water-soluble crosslinkable (meth) acrylic.
- the water-soluble polymerizable monomer (b) comprises a phosphate group-containing monofunctional (meth) acrylate compound (a), a hydrophobic crosslinkable (meth) acrylate compound (c), and a polymerization initiator (e).
- a hydrophobic crosslinkable (meth) acrylate compound (c) a polymerization initiator (e).
- e polymerization initiator
- R 1 and R 2 are each independently an alkyl group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group.
- the monofunctional (meth) acrylamide compound (b-1) has a solubility in water at 25 ° C. of preferably 10% by weight or more, more preferably 20% by weight or more, and a solubility of 30%. More preferably, it is at least wt%.
- the monofunctional (meth) acrylamide compound (b-1) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth).
- Examples include acrylamide and N-ethyl-N-methyl (meth) acrylamide.
- N, N-dimethylacrylamide and N, N-diethylacrylamide are preferable from the viewpoint of adhesion to the tooth, and N, N-diethylacrylamide is more preferable from the viewpoint of storage stability.
- the monofunctional (meth) acrylamide compound (b-1) may be blended singly or in combination.
- the water-soluble crosslinkable (meth) acrylic monomer (b-2) has at least two polymerizable groups in the molecule, has no acidic group, and has water at 25 ° C.
- the (meth) acrylic monomer means a (meth) acrylate compound and / or a (meth) acrylamide compound.
- the crosslinkable (meth) acrylic monomer (b-2) is water-soluble, it has a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, an amide group.
- a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, an amide group.
- examples of the water-soluble crosslinkable (meth) acrylic monomer (b-2) include 1,2-bis (3- (meth) acryloyloxy-2-hydroxypropyloxy) ethane, polyethylene glycol di (meth) acrylate Examples thereof include di (meth) acrylate compounds such as those having 9 or more oxyethylene groups, and water-soluble bis (meth) acrylamide compounds represented by the following general formula (2).
- X is a linear or branched aliphatic group having 1 to 6 carbon atoms, and includes —O—, —S—, —CO—O—, —CO—NH—.
- R 4 and R 5 each independently represents a hydrogen atom or carbon
- R 6 and R 7 are each independently a hydrogen atom or a methyl group.
- water-soluble cross-linkable (meth) acrylic monomers (b-2) 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane is used from the viewpoint of adhesion to teeth.
- a water-soluble bis (meth) acrylamide compound represented by the general formula (2) is preferable.
- the water-soluble crosslinkable (meth) acrylic monomer (b-2) may be blended singly or in combination.
- the water-soluble bis (meth) acrylamide compound represented by the general formula (2) is a linear or branched aliphatic group having 1 to 4 carbon atoms from the viewpoint of adhesion to teeth and polymerization curability.
- R 4 and R 5 are each independently a hydrogen atom or a linear aliphatic group having 1 to 2 carbon atoms
- X is a linear or branched aliphatic group having 2 to 4 carbon atoms. More preferably, R 4 and R 5 are each independently a hydrogen atom or a linear aliphatic group having 1 to 2 carbon atoms.
- the aliphatic group represented by X, R 4 and R 5 is preferably a saturated aliphatic group.
- R 6 and R 7 are preferably a hydrogen atom from the viewpoints of curability and availability or production.
- water-soluble bis (meth) acrylamide compound represented by the general formula (2) examples include N, N′-methylenebis (meth) acrylamide, 1,2-bis [(meth) acrylamide] ethane, 1, Examples include 3-bis [(meth) acrylamide] propane and 1,6-bis [(meth) acrylamide] hexane.
- Acrylamide] propane is preferred.
- Weight ratio of monofunctional (meth) acrylamide compound (b-1) to water-soluble crosslinkable (meth) acrylic monomer (b-2) in the present invention ((b-1) :( b-2)) Is 10: 1 to 1: 5, preferably 7: 1 to 1: 3, more preferably 5: 1 to 1: 2, and most preferably 3: 1 to 1: 1.
- the monofunctional (meth) acrylamide compound (b-1) is added in an amount of more than 10: 1, the adhesion to dentin is lowered.
- water-soluble crosslinkable (meth) acrylic monomer (b-2) is added in an amount of more than 1: 5, the adhesion to enamel is lowered.
- the amount of the water-soluble polymerizable monomer (b) is too low and too low.
- Blending amount of water-soluble polymerizable monomer (b), that is, total blending of monofunctional (meth) acrylamide compound (b-1) and water-soluble crosslinkable (meth) acrylic monomer (b-2) The amount is in the range of 10-50% by weight, preferably in the range of 20-40% by weight, based on the total weight of the dental adhesive.
- the hydrophobic crosslinkable (meth) acrylate compound (c) in the present invention has at least two polymerizable groups in the molecule, does not have an acidic group, and has a solubility in water at 25 ° C. Means less than 5% by weight of polymerizable monomer.
- the hydrophobic crosslinkable (meth) acrylate compound (c) may have a hydrophilic group, it is distinguished from the water-soluble polymerizable monomer by the solubility.
- the hydrophobic crosslinkable (meth) acrylate compound (c) improves the ambient light stability of the adhesive and extends the operation margin time under ambient light.
- Hydrophobic crosslinkable (meth) acrylate compounds (c) include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, and polymerizations of three or more functional groups. Examples thereof are sex monomers.
- aromatic compound-based bifunctional polymerizable monomers examples include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) ) Propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2 2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth)
- Examples of aliphatic compound-based bifunctional polymerizable monomers 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, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1, Examples include 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) di (meth) acrylate, and the like.
- UDMA 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate
- triethylene glycol di (meth) acrylate triethylene glycol di (meth) acrylate
- neopentyl glycol di (meth) acrylate are preferable.
- tri- or higher functional polymerizable monomers examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra ( And (meth) acrylate, 1,7-diaacryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxyheptane, and the like.
- the hydrophobic crosslinkable (meth) acrylate compound (c) may be used alone or in combination of two or more.
- the blending amount of the hydrophobic crosslinkable (meth) acrylate compound (c) is excessive, the penetrability of the dental adhesive into the tooth substance is lowered and the adhesive strength is lowered, while the blending amount is too small. In this case, the effect of adjusting the operation margin time of the dental adhesive under ambient light cannot be sufficiently obtained. Therefore, the blending amount of the crosslinkable (meth) acrylate compound (c) is in the range of 5 to 50% by weight, preferably 20 to 40% by weight, based on the total weight of the dental adhesive.
- the weight ratio ((b) :( c)) of the water-soluble polymerizable monomer (b) to the hydrophobic crosslinkable (meth) acrylate compound (c) is preferably 5: 1 to 1: 4. 3: 1 to 1: 2 is more preferable, and 2: 1 to 1: 1 is most preferable.
- the water-soluble polymerizable monomer (b) is added in an amount of more than 5: 1, the adhesive strength may be lowered because the water absorption after curing is too high.
- the hydrophobic crosslinkable (meth) acrylate compound (c) is blended more than a weight ratio of 1: 4, adhesion strength to dentin may be lowered.
- the phosphate group-containing monofunctional (meth) acrylate compounds (a), water-soluble polymerizability A polymerizable monomer other than the monomer (b) and the hydrophobic crosslinkable (meth) acrylate compound (c) may be blended.
- Such polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromo Propyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 10-hydroxydecyl (meth) Examples include acrylates and hydrophobic crosslinkable (meth) acrylamide compounds.
- the hydrophobic crosslinkable (meth) acrylamide compound has at least two (meth) acrylamide groups in the molecule, has no acidic group, and has a solubility in water at 25 ° C. of 5% by weight. Means less than the polymerizable monomer.
- These polymerizable monomers may be used alone or in combination of two or more. When the compounding amount of these polymerizable monomers is excessive, the adhesive strength may be lowered. Usually, the compounding amount of these polymerizable monomers is preferably 50% by weight or less, more preferably 30% by weight or less, and most preferably 10% by weight or less based on the total weight of the dental adhesive.
- the total amount of (meth) acrylamide compound in the dental adhesive of the present invention (monofunctional (meth) acrylamide compound (b-1), water-soluble crosslinkable (meth) acrylic monomer (b-2))
- the total amount of (meth) acrylamide group-containing compounds such as bis (meth) acrylamide compounds and hydrophobic crosslinkable (meth) acrylamide compounds) is used for dental use in terms of operating time under ambient light. Based on the total weight of the adhesive, it is preferably 50% by weight or less, and more preferably 40% by weight or less.
- Water (d) in the present invention promotes the decalcification action of the phosphate group-containing monofunctional (meth) acrylate compound (a) on the tooth. It is necessary to use water (d) that does not substantially contain impurities that adversely affect adhesiveness, and distilled water or ion-exchanged water is preferable. Adhesive strength may be reduced when the amount of water (d) is too much or too little.
- the amount of water (d) is preferably in the range of 1 to 50% by weight, more preferably in the range of 5 to 30% by weight, most preferably in the range of 10 to 20% by weight, based on the total weight of the dental adhesive. preferable.
- a known polymerization initiator can be used as the polymerization initiator (e) in the present invention.
- Specific examples include polymerization initiators such as ⁇ -diketones, ketals, thioxanthones, acylphosphine oxides, coumarins, halomethyl group-substituted s-triazine derivatives, and peroxides.
- ⁇ -diketones and acylphosphine oxides which are photopolymerization type polymerization initiators (photopolymerization initiators) are particularly preferable because they provide extremely excellent adhesive strength.
- ⁇ -diketones examples include camphorquinone, benzyl, and 2,3-pentanedione.
- ketals examples include benzyl dimethyl ketal and benzyl diethyl ketal.
- thioxanthones examples include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
- Acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) phenyl.
- Phosphine 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) phosphonate, 2,4,6-trimethylben Yl ethoxyphenyl phosphine oxide are exemplified.
- Examples of coumarins include 3,3'-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, and 3-chenoylcoumarin.
- halomethyl group-substituted s-triazine derivatives examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4, An example is 6-bis (trichloromethyl) -s-triazine.
- peroxide examples include diacyl peroxides, peroxyesters, peroxycarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides.
- diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide and the like.
- peroxyesters include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, t-butyl peroxy-2-ethylhexanoate, and the like.
- peroxycarbonates include t-butyl peroxyisopropyl carbonate.
- dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, and the like.
- peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane.
- ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like.
- hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and the like.
- the polymerization initiator (e) may be blended alone or in combination of two or more.
- the amount of the polymerization initiator (e) is preferably in the range of 0.01 to 10% by weight, more preferably in the range of 0.05 to 7% by weight, based on the total weight of the dental adhesive. A range of ⁇ 5% by weight is most preferred.
- a polymerization accelerator such as aromatic tertiary amine, aliphatic tertiary amine, sulfinic acid and its salt, aldehydes, and thiol compounds is used in combination. Also good.
- Aromatic tertiary amines include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N- Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl- 4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2 -Hydroxyethyl) -p-toluidine, N,
- Aliphatic tertiary amines include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N- Examples include methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate.
- sulfinic acid and its salts examples include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, calcium toluenesulfinate.
- aldehydes examples include dimethylaminobenzaldehyde and terephthalaldehyde.
- thiol compound examples include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.
- 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% by weight, more preferably in the range of 0.05 to 7% by weight, based on the total weight of the dental adhesive, and 0.1 to 5% by weight. % Range is most preferred.
- a water-soluble volatile organic solvent may be blended in order to improve adhesive strength, applicability, and penetrability into the tooth, and to prevent phase separation of each component.
- the water-soluble volatile organic solvent usually has a boiling point of 150 ° C. or lower under normal pressure and a water solubility at 25 ° C. of 5% by weight or more, more preferably 30% by weight or more, and most preferably any An organic solvent that is soluble in water at a rate is used.
- ethanol methanol
- 1-propanol isopropyl alcohol
- acetone methyl ethyl ketone
- 1,2-dimethoxyethane 1, Examples include 2-diethoxyethane and tetrahydrofuran.
- the water-soluble volatile organic solvent may be used alone or in combination of two or more. If the amount of the water-soluble volatile organic solvent is excessive, the adhesive strength may be reduced.
- the blending amount of the water-soluble volatile organic solvent is preferably 1 to 70% by weight, more preferably 5 to 50% by weight based on the total weight of the dental adhesive, and 10 to 30% by weight. Most preferred.
- a filler may be blended in order to improve adhesive strength, applicability, fluidity, radiopacity and mechanical strength.
- One type of filler may be blended, or a plurality of types may be blended in combination.
- Examples of the filler include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.
- 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 may be used after being surface-treated 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.
- a fine particle filler having a primary particle diameter of 0.001 to 0.1 ⁇ m is preferably used in terms of adhesive strength, coating property, and the like. Specific examples include “Aerosil OX50”, “Aerosil 50”, “Aerosil 200”, “Aerosil 380”, “Aerosil R972”, “Aerosil 130” (all of which are trade names manufactured by Nippon Aerosil Co., Ltd.). .
- the blending amount of the filler is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 0.5 to 20% by weight, and in the range of 1 to 10% by weight based on the total weight of the dental adhesive. Most preferred.
- a fluorine ion releasing substance may be blended to impart acid resistance to the tooth.
- Fluorine ion-releasing substances include fluorine glasses such as fluoroaluminosilicate glass; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride; methyl methacrylate and methacryl Fluorine ion releasing polymers such as copolymers with acid fluoride; fluorine ion releasing substances such as cetylamine hydrofluoride are exemplified.
- a stabilizer polymerization inhibitor
- a colorant e.g., a fluorescent agent
- an ultraviolet absorber e.g., 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 adhesive according to the present invention is applied to the tooth to be treated using a sponge or brush, and in that state, 0 seconds (that is, the following air blow is performed immediately after application) to 120 seconds, preferably 1 Allow to stand for ⁇ 60 seconds, more preferably 3 to 30 seconds, most preferably 5 to 20 seconds, or continue rubbing on the tooth surface with a sponge or the like within 60 seconds.
- a composite restorative material such as composite resin, cement, or pit and fissure filling material is applied to the application surface of the dental adhesive, and both are cured simultaneously. .
- the dental adhesive according to the present invention contains, as a polymerization initiator (e), a photopolymerization type polymerization initiator (photopolymerization initiator) that generates radicals by light irradiation, a filling restorative material is used.
- a polymerization initiator e
- photopolymerization type polymerization initiator photopolymerization initiator
- a filling restorative material Prior to application, it is preferable to irradiate the dental adhesive applied to the surface of the tooth with light using a dental visible light irradiator or the like, so as to obtain a better adhesive force.
- the dental adhesive according to the present invention basically does not need to be pretreated with a phosphoric acid etchant before being applied to a tooth, but even when pretreated with a phosphoric acid etchant, High adhesion is exhibited.
- the dental adhesive according to the present invention exhibits an excellent adhesive force not only for the tooth quality but also for a crown restoration material (metal, porcelain, ceramics, composite cured product, etc.) broken in the oral cavity.
- a crown restoration material metal, porcelain, ceramics, composite cured product, etc.
- the dental adhesive according to the present invention is a primer such as a commercially available primer for metal bonding, a primer for porcelain bonding, or hypochloric acid. You may use it in combination with tooth surface cleaning agents, such as salt and hydrogen peroxide solution.
- DAAA diacetone acrylamide (water-soluble monofunctional acrylamide compound represented by the following general formula)
- TCDAA Hydrophobic crosslinkable acrylamide compound represented by the following general formula
- BHT 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))
- Example 1 MDP (10 parts by weight), DEAA (27 parts by weight), BAAP (3 parts by weight), Bis-GMA (25 parts by weight), distilled water (15 parts by weight), ethanol (20 parts by weight), , CQ (2 parts by weight), BAPO (0.1 parts by weight), DABE (1 part by weight), R972 (5 parts by weight), and BHT (0.05 parts by weight)
- An adhesive was prepared.
- a test piece is prepared according to the following adhesive test piece preparation method, and the adhesive strength and adhesion durability are determined according to the following adhesive strength test method and adhesive durability test method. I investigated.
- the dental adhesive prepared in the same manner was stored in a thermostat at 50 ° C.
- Adhesion test piece preparation method The front teeth of the cow are smoothly wet-polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) to expose the enamel surface or dentin surface, and then water on the surface is blown off using a dental air syringe.
- Adhesive tape with a thickness of about 150 ⁇ m with a 3 mm diameter round hole is applied to the exposed enamel surface or dentin surface, and a dental adhesive is applied to the round hole with a brush and left for 20 seconds. Then, using a dental air syringe, dry until the dental adhesive is no longer fluid.
- a dental light irradiator (trade name “Pencure 2000” manufactured by Morita).
- a photopolymerizable composite resin (Kuraray Medical, trade name “Clear Fill AP-X”) is placed on the dental adhesive, and a release film (Kuraray, trade name “EVAL”) is placed.
- a slide glass is placed on the release film and pressed, and irradiated with light for 20 seconds using a dental light irradiator “Pencure 2000” to be cured.
- Adhesion test method The test piece prepared by the above-mentioned method for preparing an adhesive test piece is immersed in distilled water in a sample container and left in a thermostat set at 37 ° C. for 24 hours, and then the adhesive strength is measured.
- adhesive strength tensile adhesive strength
- a universal testing machine Instron
- the numerical value of the adhesive strength is the average value of the measured values of 8 test pieces (eight exposed enamel surfaces and 8 exposed dentin surfaces).
- Adhesion durability test method The test piece prepared by the above-described method for preparing an adhesive test piece was immersed in distilled water in a sample container and left in a thermostat set at 37 ° C. for 24 hours, and then further cooled at 4 ° C. and 60 ° C. The adhesive strength is measured after applying a thermal cycle of immersing in warm water of 1 minute each for 4000 minutes.
- adhesive strength tensile adhesive strength
- a universal testing machine Instron
- the numerical value of the adhesive strength is the average value of the measured values of 8 test pieces (eight exposed enamel surfaces and 8 exposed dentin surfaces).
- ⁇ Operation allowance time under ambient light is generally 30 seconds or longer, and can be used without problems in clinical practice.
- Examples 2-6 and Comparative Examples 1-2 Seven types of dental adhesives shown in Table 1 were prepared, and their adhesive strength, adhesion durability, storage stability, and operation margin time under ambient light were examined. Table 1 shows the blending ratio (parts by weight) of each dental adhesive and the test results.
- Example 5 A dental adhesive was prepared as TCDAA (25 parts by weight) instead of Bis-GMA (25 parts by weight) in the dental adhesive of Example 2, and the adhesive strength, adhesion durability, storage stability and environment were prepared. We investigated the operating margin under light. Table 1 shows the blending ratio (parts by weight) of each dental adhesive and the test results.
- the dental adhesives according to the present invention (Examples 1 to 6) exhibited excellent adhesive strength and adhesion durability with respect to both enamel and dentin. The decrease in strength is small. From this, it can be seen that the dental adhesive according to the present invention has excellent adhesion, adhesion durability and storage stability. Moreover, it turns out that the dental adhesive which concerns on this invention has the moderate operation allowance time under environmental light.
- Comparative Examples 1 and 2 have low adhesive strength and adhesion durability to either enamel or dentin. Low adhesion strength to either quality or dentin. From this, it can be seen that the dental adhesives of Comparative Examples 1 and 2 are insufficient in adhesion, adhesion durability and storage stability with respect to either enamel or dentin. Further, the dental adhesive of Comparative Example 3 that does not contain a water-soluble crosslinkable (meth) acrylic monomer has a lower adhesive force to the dentin than the dental adhesive of Example 2, and the dentin The adhesion durability and adhesion strength of the stored product to dentin are also low.
- the dental adhesive of Comparative Example 3 has insufficient adhesion to dentin, adhesion durability and storage stability.
- the dental adhesive of Comparative Example 4 in which a hydrophobic crosslinkable (meth) acrylamide was blended without blending a water-soluble crosslinkable (meth) acrylic monomer has an adhesive strength against dentin. Both the adhesive durability and the adhesive strength of stored products are low. From this, it can be seen that the dental adhesive of Comparative Example 4 has insufficient adhesion to dentin, adhesion durability and storage stability.
- the dental adhesive of Comparative Example 5 in which the hydrophobic crosslinkable (meth) acrylate is not blended but the hydrophobic crosslinkable (meth) acrylamide is blended has the adhesive strength, the adhesion durability, and the adhesive strength of the stored product. However, both are lower than the dental adhesive of Example 2. Moreover, it can be seen that the dental adhesive of Comparative Example 5 has a very short operation margin under ambient light, and the stability under ambient light is not sufficient.
- the dental adhesive of Comparative Example 7 in which 6-MHPA, which is an acidic group-containing monofunctional (meth) acrylate compound other than a phosphate group, was blended in place of MDP, which is a phosphate group-containing monofunctional (meth) acrylate compound Have low adhesion strength, adhesion durability and adhesion strength of stored products against enamel. From this, it can be seen that the dental adhesive of Comparative Example 7 has insufficient adhesion to enamel, adhesion durability and storage stability.
- Example 7 to 13 Seven types of dental adhesives shown in Table 2 were prepared, and the adhesive strength, adhesion durability, storage stability, and operation margin time under ambient light were examined. Table 2 shows the blending ratio (parts by weight) of each dental adhesive and the test results.
- the dental adhesives according to the present invention (Examples 7 to 13) exhibited excellent adhesive strength and adhesion durability for both enamel and dentin, The decrease in strength is small. From this, it can be seen that the dental adhesive according to the present invention has excellent adhesion, adhesion durability and storage stability. Moreover, it turns out that the dental adhesive which concerns on this invention has the moderate operation allowance time under environmental light.
- a dental adhesive containing a (meth) acrylamide compound (DAAA) not included in the monofunctional (meth) acrylamide compound (b-1) in the present invention has a high adhesive strength for non-storage products, but enamel Or the adhesive durability with respect to dentin is low, and the adhesive strength with respect to the enamel of a stored article is also low. From this, it can be seen that the dental adhesives of Comparative Examples 8 to 10 are not sufficient in terms of adhesion durability and storage stability.
- Example 3 Five types of dental adhesives shown in Table 3 were prepared, and their adhesive strength, adhesion durability, storage stability, and operation margin time under ambient light were examined. Table 3 shows the mixing ratio (parts by weight) of each dental adhesive and the test results.
- the dental adhesives according to the present invention (Examples 14 to 16) exhibited excellent adhesive strength and adhesion durability for both enamel and dentin, The decrease in strength is small. From this, it can be seen that the dental adhesive according to the present invention has excellent adhesion, adhesion durability and storage stability. Moreover, it turns out that the dental adhesive which concerns on this invention has the moderate operation allowance time under environmental light.
- Comparative Example 11 has a slightly lower adhesive force to dentin, and Comparative Example 12 has an enamel, Adhesive strength is low for both dentin. Moreover, both the comparative examples 11 and 12 have low adhesion durability to enamel and dentin. Regarding the adhesive strength of stored goods, Comparative Example 11 has low adhesive strength to dentin, and Comparative Example 12 has low adhesive strength for both enamel and dentin. Therefore, Comparative Example 11 has a slightly low adhesion to dentin, and adhesion durability and storage stability are not sufficient, and Comparative Example 12 has insufficient adhesion strength, adhesion durability and storage stability. I understand that.
- the dental adhesives according to the present invention showed excellent adhesive strength and adhesion durability for both enamel and dentin, and the adhesion of stored items. The decrease in strength is small. From this, it can be seen that the dental adhesive according to the present invention has excellent adhesion, adhesion durability and storage stability. Moreover, it turns out that the dental adhesive which concerns on this invention has the moderate operation allowance time under environmental light.
- the one-pack type dental adhesive according to the present invention when repairing a dental material (enamel, dentin and cementum) damaged by caries or the like, a dental material, a dental composite resin, a dental compomer, It can be used for bonding with dental restorative materials such as dental resin cements.
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Abstract
Description
10~50重量%の水溶性の重合性単量体(b)、
5~50重量%の疎水性の架橋性(メタ)アクリレート化合物(c)、
水(d)、及び
重合開始剤(e)を含有してなり、
前記水溶性の重合性単量体(b)が、下記一般式(1)で表される単官能(メタ)アクリルアミド化合物(b-1)及び水溶性の架橋性(メタ)アクリル系単量体(b-2)の組み合わせであり、前記単官能(メタ)アクリルアミド化合物(b-1)と前記水溶性の架橋性(メタ)アクリル系単量体(b-2)の重量比が10:1~1:5である、
1液型の歯科用接着剤である。
MDP:10-メタクリロリルオキシデシルジハイドロジェンホスフェート
MHP:6-メタクリロイルオキシヘキシルジハイドロジェンホスフェート
GPDM:1,3-ジメタクリロイルオキシプロピル-2-ジハイドロジェンホスフェート
6-MHPA:6-メタクリロキシヘキシル-ホスホノアセテート
DEAA:N,N-ジエチルアクリルアミド
DMAA:N,N-ジメチルアクリルアミド
DAAA:ジアセトンアクリルアミド(下記の一般式で表される水溶性の単官能アクリルアミド化合物)
BAAP:1,3-ビス(アクリルアミド)プロパン
MBAA:N,N’-メチレンビスアクリルアミド
BAAE:1,2-ビス(アクリルアミド)エタン
BAAH:1,6-ビス(アクリルアミド)ヘキサン
#801:1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロピルオキシ)エタン
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
UDMA:〔2,2,4-トリメチルヘキサメチレンビス(2-カルバモイルオキシエチル)〕ジメタクリレート
3G:トリエチレングリコ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
TCDAA:下記の一般式で表される疎水性の架橋性アクリルアミド化合物
CQ:dl-カンファーキノン
BAPO:ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキサイド
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
DABE:4-N,N―ジメチルアミノ安息香酸エチル
R972:アエロジル社製の微粒子シリカ
BHT:2,6-ジ-t-ブチル-4-メチルフェノール(安定剤(重合禁止剤))
MDP(10重量部)と、DEAA(27重量部)と、BAAP(3重量部)と、Bis-GMA(25重量部)と、蒸留水(15重量部)と、エタノール(20重量部)と、CQ(2重量部)と、BAPO(0.1重量部)と、DABE(1重量部)と、R972(5重量部)と、BHT(0.05重量部)とを混合して、歯科用接着剤を調製した。次いで、調製直後の歯科用接着剤(非貯蔵品)について、下記の接着試験片作製方法に従って試験片を作製し、下記の接着力試験方法及び接着耐久性試験方法に従って、接着力及び接着耐久性を調べた。また、同様に調製した歯科用接着剤を50℃の恒温器に30日間貯蔵し、下記の貯蔵安定性試験方法により、貯蔵安定性を調べた。また、調製直後の歯科用接着剤(非貯蔵品)について、下記の操作余裕時間の試験方法により、環境光下での操作余裕時間を調べた。(なお、その他の実施例及び比較例で調べた接着力、接着耐久性、貯蔵安定性、及び環境光下での操作余裕時間も、それぞれ同じ試験方法により調べたものである。)表1に、この歯科用接着剤の配合比(重量部)及び試験結果を示す。
牛の前歯を#1000シリコン・カーバイド紙(日本研紙社製)で平滑に湿潤研磨してエナメル質表面又は象牙質表面を露出させた後、表面の水を歯科用エアーシリンジを用いて吹き飛ばす。露出したエナメル質表面又は象牙質表面に、直径3mmの丸穴を有する厚さ約150μmの粘着テープを貼着し、丸穴に歯科用接着剤を筆を用いて塗布し、20秒間放置した後、歯科用エアーシリンジを用いて当該歯科用接着剤の流動性が無くなるまで乾燥する。次いで、歯科用光照射器(モリタ社製、商品名「ペンキュア2000」)を用いて10秒間光照射を行う。次いで、その歯科用接着剤の上に光重合型コンポジットレジン(クラレメディカル社製、商品名「クリアフィルAP-X」)を載置し、離型フィルム(クラレ社製、商品名「エバール」)を被せた後、その離型フィルムの上にスライドガラスを載置して押しつけ、歯科用光照射器「ペンキュア2000」を用いて20秒間光照射して、硬化させる。次いで、この硬化面に対して、歯科用レジンセメント(クラレメディカル社製、商品名「パナビア21」)を用いて、直径5mm、長さ1.5cmのステンレス製の円柱棒の一方の端面(円形断面)を接着し、30分間静置して、試験片とする。
上記の接着試験片作製方法により作製した試験片を、サンプル容器内の蒸留水に浸漬した状態で、37℃に設定した恒温器内に24時間放置した後、接着強度を測定する。接着強度(引張接着強度)の測定には万能試験機(インストロン社製)を用い、クロスヘッドスピードを2mm/分に設定して測定する。接着強度の数値は、それぞれ8個(エナメル質表面を露出させたもの8個、象牙質表面を露出させたもの8個)の試験片についての測定値の平均値とする。
上記の接着試験片作製方法により作製した試験片を、サンプル容器内の蒸留水に浸漬した状態で、37℃に設定した恒温器内に24時間放置した後、更に4℃の冷水中と60℃の温水中に各1分間ずつ浸漬する熱サイクルを4000回負荷させた後に接着強度を測定する。接着強度(引張接着強度)の測定には万能試験機(インストロン社製)を用い、クロスヘッドスピードを2mm/分に設定して測定する。接着強度の数値は、それぞれ8個(エナメル質表面を露出させたもの8個、象牙質表面を露出させたもの8個)の試験片についての測定値の平均値とする。
50℃の恒温器に30日間貯蔵した歯科用接着剤(貯蔵品)について、上記の接着試験片作製方法に従って試験片を作製し、上記の接着力試験方法により接着強度を測定する。
暗室内において、色温度変換フィルム及び紫外線フィルタが挿入されたキセノンランプの下で、照度が8000ルクスとなる様な高さに混和皿(クラレメディカル社製、品番「#902(B)」)を置き、歯科用接着剤(非貯蔵品)を1滴滴下する。一定時間の間、試料を光に曝した後、試料の滴下された混和皿を照射域から取り出して、直ちに試料が物理的に均一であるか検査し、均一性を保持した時間を操作余裕時間とする。
表1に示す7種の歯科用接着剤を調製し、それぞれの接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例2の歯科用接着剤中のBAAP(10重量部)を配合しない歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例2の歯科用接着剤中のBAAP(10重量部)に代えて、TCDAA(10重量部)とした歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例2の歯科用接着剤中のBis-GMA(25重量部)に代えて、TCDAA(25重量部)とした歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例2の歯科用接着剤中のMDP(10重量部)に代えて、GPDM(10重量部)とした歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例2の歯科用接着剤中のMDP(10重量部)に代えて、6-MHPA(10重量部)とした歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表1に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
表2に示す7種の歯科用接着剤を調製し、それぞれの接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表2に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
実施例11~13の歯科用接着剤中のDMAAに代えて、DAAAをそれぞれ同配合量とした歯科用接着剤を調製し、接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表2に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
表3に示す5種の歯科用接着剤を調製し、それぞれの接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表3に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
表4に示す11種の歯科用接着剤を調製し、それぞれの接着力、接着耐久性、貯蔵安定性及び環境光下での操作余裕時間を調べた。表4に、各歯科用接着剤の配合比(重量部)及び試験結果を示す。
Claims (4)
- 1~30重量%のリン酸基含有単官能(メタ)アクリレート化合物(a)、
10~50重量%の水溶性の重合性単量体(b)、
5~50重量%の疎水性の架橋性(メタ)アクリレート化合物(c)、
水(d)、及び
重合開始剤(e)を含有してなり、
前記水溶性の重合性単量体(b)が、下記一般式(1)で表される単官能(メタ)アクリルアミド化合物(b-1)及び水溶性の架橋性(メタ)アクリル系単量体(b-2)の組み合わせであり、前記単官能(メタ)アクリルアミド化合物(b-1)と前記水溶性の架橋性(メタ)アクリル系単量体(b-2)の重量比が10:1~1:5である、
1液型の歯科用接着剤。
- 前記水(d)の配合量が1~50重量%であり、前記重合開始剤(e)の配合量が0.01~10重量%である請求項1に記載の1液型の歯科用接着剤。
- 前記水溶性の架橋性(メタ)アクリル系単量体(b-2)が、下記一般式(2)で表される水溶性のビス(メタ)アクリルアミド化合物及び1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロピルオキシ)エタンからなる群より選ばれる少なくとも1種である請求項1に記載の1液型の歯科用接着剤。
- 前記単官能(メタ)アクリルアミド化合物(b-1)が、N,N-ジエチルアクリルアミドである請求項1に記載の1液型の歯科用接着剤。
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JP2014507391A JP5860137B2 (ja) | 2012-03-30 | 2013-03-15 | 1液型の歯科用接着剤 |
CN201380017795.0A CN104185468B (zh) | 2012-03-30 | 2013-03-15 | 单组分的牙科用粘合剂 |
US14/387,396 US9700491B2 (en) | 2012-03-30 | 2013-03-15 | One-part dental adhesive |
EP13769369.3A EP2835128B1 (en) | 2012-03-30 | 2013-03-15 | One-pack dental adhesive |
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JP2016008211A (ja) * | 2014-06-26 | 2016-01-18 | クラレノリタケデンタル株式会社 | 歯科用修復材組成物 |
WO2023042716A1 (ja) * | 2021-09-17 | 2023-03-23 | 三井化学株式会社 | (メタ)アクリルアミド化合物の製造方法 |
WO2023042715A1 (ja) * | 2021-09-17 | 2023-03-23 | 三井化学株式会社 | (メタ)アクリルアミド化合物、モノマー組成物、歯科材料用組成物及び歯科材料 |
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AU2016365959B2 (en) * | 2015-12-07 | 2021-09-16 | Kuraray Noritake Dental Inc. | Dental adhesive |
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