Classifications

• • 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
  • A61K6/80—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 is a single-component dental adhesive composition which exhibits excellent adhesion to both materials of a dental ceramics and an organic composite containing an inorganic compound (hereinafter, referred to as composite material in some cases), and is excellent in can-stability.
• inorganic materials, and composites of inorganic-organic composite materials are used in many cases, a representative of which is a dental porcelain (main component is silicon dioxide), an alumina core, a zirconia core, and a composite.
• the composite is obtained by mixing an inorganic powder and a resin into a paste.
• metal materials are also used.
• silane coupling agent is known to improve adhesion to a material containing silicon dioxide as a main component
• acidic monomer is known to improve adhesion to a material containing alumina and zirconia as a main component.
• JP-A No. 63-51308 and JP-A No. 7-277913 disclose a dental adhesive composition for adhering a dental porcelain containing silicon dioxide, and a dental restorative material such as a dental resin, a dental alloy and the like by combining a silane coupling agent and a phosphoric acid ester monomer.
• silane coupling agent and the acidic monomer coexist, and they must be mixed before use.
• JP-A No. 9-137129 discloses a dental adhesive composition obtained from a coating material consisting of a coating solution containing a silane coupling agent and an acidic compound such as organic carboxylic acid and the like, and a polymerizable monomer which is coated on a coating surface of the coating solution and is polymerized in the presence of a polymerization catalyst, but since this dental adhesive composition has little adhesion to aluminum oxide and zirconium oxide, it is necessary to select an adherend.
• JP-A No. 2006-45179 discloses a dental adhesive composition for adhering a dental material consisting of an inorganic compound, or an organic composite containing an inorganic compound, and a dental adhesive composition having adhesion to aluminum oxide and zirconium oxide is proposed.
• a silane coupling agent is deteriorated by a phosphonic acid group-containing (meth)acrylate-based monomer, and it is difficult to stably exhibit the adhering effect for a long period of time. And, it is difficult that the silane coupling agent and the acidic monomer coexist, and they must be mixed before use.
• JP-A No. 2006-45094 describes a two-component mixed type primer composition for improving adhesiveness by pre-treating a surface to be adhered of a prosthesis consisting of a cured dental composite material before application of the adhering material upon adhesion of a cured product of a dental composite material and a dental material.
• this adhesive has no adhesion to a porcelain, and has a primer composition such that two components must be mixed before adhesion.
• JP-A No. 2000-248201 discloses a composition which exhibits sufficient adhesion to any of a base metal alloy, a noble alloy, and a ceramics, but when a silane coupling agent and an acidic group-containing polymerizable polymer are used as a single-component composition, a serious defect arises regarding can-stability of the single-component composition.
• JP-A No. 2002-265312 discloses the technique of composition which exhibits sufficient adhesion to any of a tooth substance, a base metal alloy, a noble metal alloy, and a ceramics, but when a silane coupling agent and an acidic group-containing polymerizable monomer are used as a single-component composition, a serious defect arises regarding can-stability of the single-component composition.
• Patent Publication 1 JP-A No. 63-51308
• Patent Publication 2 JP-A No. 7-277913
• Patent Publication 3 JP-A No. 9-137129
• Patent Publication 4 JP-A No. 2006-45179
• Patent Publication 5 JP-A No. 2006-45094
• Patent Publication 6 JP-A No. 2000-248201
• Patent Publication 7 JP-A No. 2000-265312
• An object of the present invention is to exhibit excellent adhesion to both materials of a dental ceramics and an organic composite containing an inorganic compound. Particularly, an object of the present invention is to respond to demand of a material having an improved adhesive power with a single-component, without selecting silica-based, alumina-based, zirconia-based, and metal-based materials.
• a further object is to provide a dental adhesive composition having good handling property which is mostly desired by users for the purpose of shortening a working time, reducing a technical error or the like, that is, provide a single-component dental adhesive composition.
• the present invention responds to demand of a single-component dental adhesive composition prepared by formulating a silane coupling agent and an acidic group-containing polymerizable monomer into the same solution.
• the single-component dental adhesive composition is typified by a dental primer, a dental adhesive, and a dental adhesive restorative material.
• the present invention was done in order to solve the aforementioned problems, and is a single-component dental adhesive composition comprising 1 to 60 parts by weight of (a) a silane coupling agent, 1.0 to 20.0 parts by weight based on 100 parts by weight of the (a) component of (b) an acidic group-containing polymerizable monomer, and 28 to 99 parts by weight of (c) a volatile organic solvent.
• the present invention is a one-component dental primer comprising (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, and (c) a volatile organic solvent,
• the dental primer comprises 1 to 60 parts by weight of (a) a silane coupling agent, 1.0 to 20.0 parts by weight based on 100 parts by weight of the (a) component of (b) an acidic group-containing polymerizable monomer, and 28 to 99 parts by weight of (c) a volatile organic solvent.
• the present invention is a one-component dental primer comprising (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, and (c) a volatile organic solvent,
• the (b) acidic group-containing polymerizable monomer is a phosphonic acid group-containing (meth)acrylate-based monomer
• the phosphonic acid group-containing (meth)acrylate-based monomer is represented by the following general formula (I):
• R 1 denotes a hydrogen atom or a methyl atom
• R 2 denotes an alkylene group of a carbon number of 1 to 20 optionally having a substituent
• R 3 denotes an alkylene group of a carbon number of 1 to 15 optionally having substituent
• the present invention is a one-component dental adhesive comprising a radical polymerizable monomer, (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, and a photopolymerization initiator,
• the present invention is a one-component dental adhesive comprising a radical polymerizable monomer, (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, and a photopolymerization initiator,
• the acidic group-containing polymerizable monomer is a phosphonic acid group-containing (meth)acrylate-based monomer
• the phosphonic acid group-containing (meth)acrylate-based monomer is represented by the following general formula (I):
• R 1 denotes a hydrogen atom or a methyl atom
• R 2 denotes an alkylene group of a carbon number of 1 to 20 optionally having a substituent
• R 3 denotes an alkylene group of a carbon number of 1 to 15 optionally having a substituent
• the present invention is a one-component dental adhesive restorative material comprising a radical polymerizable monomer, (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, a photopolymerization initiator, and a filler,
• the present invention is a one-component dental adhesive restorative material comprising a radical polymerizable monomer, (a) a silane coupling agent, (b) an acidic group-containing polymerizable monomer, a photopolymerization initiator, and a filler,
• the acidic group-containing polymerizable monomer is a phosphonic acid group-containing (meth)acrylate-based monomer
• the phosphonic acid group-containing (meth)acrylate-based monomer is represented by the following general formula (I):
• R 1 denotes a hydrogen atom or a methyl atom
• R 2 denotes an alkylene group of a carbon number of 1 to 20 optionally having a substituent
• R 3 denotes an alkylene group of a carbon number of 1 to 15 optionally having a substituent
• Adoption of such the construction results in excellent adhesiveness and durability on each of a dental ceramics, and an organic composite containing an inorganic compound, which has not previously been seen, and handling is simple, and can-stability is excellent.
• silane coupling agent is characterized by being represented by the following general formula [2].
• R 1 represents an organic residue having at least one functional group selected from the group consisting of a (meth)acryloyl group, a vinyl group, a styryl group, a mercapto group, and an epoxy group
• R 2 represents a hydroxy group, an alkyl group of a carbon number of 1 to 5 or an alkoxy group of a carbon number of 1 to 5
• R 3 and R 4 each represent a hydroxy group or an alkoxy group of a carbon number of 1 to 5
• a preferable (a) silane coupling agent is a compound in which, in the general formula [2], R 1 is an organic residue having at least one functional group selected from the group consisting of a (meth)acryloyl group, and a vinyl group, R 2 is a hydroxy group, an alkyl group of a carbon number of 1 to 5 or an alkoxy group of a carbon number of 1 to 5, and R 3 and R 4 each are a hydroxy group or an alkoxy group of a carbon number of 1 to 5.
• the acidic group-containing polymerizable monomer is characterized in that it is 4-(meth)acryloxyethyltrimellitic acid, 4-(meth)acryloxyethyltrimellitic acid anhydride, 6-(meth)acryloxyhexyl phosphonoacetate, 6-(meth)acryloxyhexyl phosphonopropionate, or 10-(meth)acryloxydecyl hydrogen phosphate.
• the volatile organic solvent is characterized in that it is methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, isopropyl ether, or a radical-polymerizable monomer such as (meth)acrylic acid ester, (meth)acrylamide, vinyl ester or the like.
• the dental adhesive composition of the present invention By using the dental adhesive composition of the present invention, excellent adhesiveness and durability can be exhibited on both materials of a dental ceramics, and an organic composite containing an inorganic compound and, further, can-stability is excellent, and handling is simple. Particularly, adhesion on silica-based, alumina-based and zirconia-based dental materials, and non-noble metals, and inorganic organic composites is excellent.
• the composition is used in adhesion with a resin-based material when any of a dental restoration/a dental restorative material/a dental device is a dental ceramics containing silicon dioxide as a main component, a dental ceramics containing aluminum dioxide and zirconium dioxide as a main component, a resin-based material containing a ceramics or an inorganic filler, or a dental restoration made of a non-metal material, in adhesion between any of a dental restoration/a dental restorative material/a dental device.
• the dental adhesive restorative material is such that a dental restorative material itself is made to have adhesiveness using the technique of the present invention.
• the material is an adhesive composite resin for a facing crown or fracture restoration.
• the dental adhesive composition of the present invention By using the dental adhesive composition of the present invention, a dentist can simply implement an adhering work without selecting an adherend.
• a handling method is entirely the same as that of various adhesive compositions which have been used until now. That is, although the composition is an adhesive composition having essentially entirely new function, since the using method is the same, it is easily accepted by a dentist who is a user, and is advantageous to whole dental therapy.
• the dental adhesive composition in the present invention is a one-component adhesive composition
• handling is simple.
• a mixing procedure was necessary upon use, a procedure was troublesome, working was time-consuming, and many points were unknown, as whether an appropriate mixing ratio of two components is maintained, and a sufficient mixing procedure has been done or not was unclear, and a technical error was easily generated, causing a loss.
• the present invention can be also used as a primer, and can be also used simultaneously with other adhesive.
• a specific embodiment in the dental adhesive composition of the present invention is a single-component dental ceramics, a dental primer of an organic composite containing an inorganic compound, a dental adhesive, and a dental adhesive restorative material.
• An adhesive composite resin is included in a dental adhesive restorative material, and a resin cement is included in a dental adhesive.
• high adhesiveness can be exhibited by extremely simple treatment in use as a single-component dental primer of an organic composite containing a dental ceramics, or an inorganic compound.
• the dental adhesive composition of the present invention is excellent in use in a dental bonding agent which is a dental adhesive, an orthodontic adhesive, a resin cement, and a dual curing-type resin cement.
• a dental bonding agent which is a dental adhesive, an orthodontic adhesive, a resin cement, and a dual curing-type resin cement.
• the composition can be used in an opaque agent, a compomer, a resin core, an adhesive composite resin, a facing crown material or the like.
• silane coupling agent having a functional group which can be copolymerized with or form a chemical bond with a polymerizable monomer component in a dental adhesive composition and an adherend material, as (a) the silane coupling agent used in the present invention, in order to obtain good adhesion to a ceramics material.
• a silane coupling agent satisfying this condition a silane compound represented by the general formula [2] is used.
• a (meth)acryloyl group, a vinyl group, and a styryl group are connected to a polymer of (meth)acrylic acid ester monomer by copolymerization with a (meth)acrylic acid ester monomer, and a mercapto group is connected to a polymer of a (meth)acrylic acid ester monomer by formation of a chemical bond derived from a chain transfer/stopping reaction, and an epoxy group is connected to a polymer of a (meth)acrylic acid ester monomer by forming a chemical bond with a monomer having an amino group or a carboxyl group reactive therewith.
• R2, R3 and R4 are each a lower alkoxy group of a carbon number of 1 to 5 or a hydroxy group, provided that R2 may be an alkyl group of a carbon number of 1 to 5.
• Specific examples of the silane coupling agent satisfying the aforementioned condition include the following:
• a preferable (a) silane coupling agent is a compound in which, in the general formula [2], R 1 is an organic residue having at least one functional group selected from the group consisting of a (meth)acryloyl group, and a vinyl group, R 2 is a hydroxy group, an alkyl group of a carbon number of 1 to 5 or an alkoxy group of a carbon number of 1 to 5, and R 3 and R 4 are each a hydroxy group or an alkoxy group of a carbon number of 1 to 5.
• a particularly preferable (a) silane coupling agent is 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
• a blending ratio of (a) the silane coupling agent may be appropriately used depending on the use purpose of the composition, and is adjusted in the range of 1 to 60 parts by weight, preferably adjusted in the range of 5.0 to 50 parts by weight.
• acidic group-containing polymerizable monomer in the present invention all polymerizable monomers which have previously been used as a dental acidic group-containing polymerizable monomer can be used and, particularly, monomers can be used by selecting from polymerizable monomers having a carboxyl group, phosphoric acid ester group, a phosphonic acid group, a pyrophosphoric acid group, or a sulfonic acid group in the molecule.
• examples of the monomer containing carboxyl group in the molecule include methacrylic acid, 4-(meth)acryloxyethyltrimellitic acid, 4-(meth) acryloyloxyethoxycarbonylphthalic acid, 4-(meth) acryloyloxybutyloxycarbonylphthalic acid, 4-(meth) acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth) acryloyloxyoctyloxycarbonylphthalic acid, 4-(meth) acryloyloxydecyloxycarbonylphthalic acid, maleic acid, and an acid anhydride thereof, 5-(meth) acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 7-(meth)acryloyloxy-1,1-heptanedicarboxylic acid,
• examples of the monomer containing a phosphoric ester group, a phosphonic acid group, or a pyrophosphoric acid group in the molecule include polymerizable monomers such as 3-(meth)acryloxypropyl-3-phosphonopropionate, 3-(meth)acryloxypropyl-3-phosphonoacetate, 4-(meth)acryloxybutyl-3-phosphonopropionate, 4-(meth) acryloxybutylphosphonoacetate, 5-(meth)acryloxypentylphosphono-3-propionate, 5-(meth)acryloxypentyl-3-phosphonoacetate, 6-(meth)acryloxyhexyl-3-phosphonopropionate, 6-(meth)acryloxyhexyl-3-phosphonoacetate, 10-(meth)acryloxydecyl-3-phosphonopropionate, 10-(meth)acryloxydecyl-3-phosphonopropionate, 10-(meth)acryloxydecyl-3-phosphono
• examples of the monomer having a sulfonic acid group in the molecule include styrenesulfonic acid, 2-sulfoethyl(meth)acrylate, 6-sulfohexyl(meth)acrylate, 10-sulfodecyl(meth)acrylate, 2-(meth)acrylamide-2-methylpropanesulfonic acid and the like and, furthermore, acid chlorides, alkali metal salts, alkaline earth metal salts and ammonium salts thereof.
• a preferable polymerizable monomer is a (meth)acrylate-based monomer containing a phosphonic acid group represented by:
• (meth)acrylate means acrylate or methacrylate.
• Preferable examples include (meth)acrylate represented by the following general formula [1]:
• R 1 denotes a hydrogen atom or a methyl group
• R 2 denotes an alkylene group of a carbon number of 1 to 20 optionally having a substituent
• R 3 denotes an alkylene group of a carbon number of 1 to 15 optionally having a substituent
• the alkylene group include those described for the general formula [1].
• a substituent which may bind to R 2 or R 3 there are unsaturated groups such as an alkenyl group and an alkynyl group, an alkyl group, and an alkyl group bound to a phenyl group.
• alkenyl group examples include:
• examples of the alkyl group include —CH 3 , —C 2 H 5 , and —C 3 H 7
• examples of the alkyl group bound to a phenyl group include —CH 2 CH 2 OC 6 H 5 .
• Examples of a specific compound represented by the general formula [1] include the following compounds:
• a particularly preferable phosphonic acid group-containing (meth)acrylate-based monomer is 6-methacryloxyhexyl-phosphonoacetate, 6-methacryloxyhexyl-3-phosphonopropionate, 10-methacryloxydecyl-3-phosphonopropionate, and 10-methacryloxydecyl-phosphonoacetate, and a particularly preferable phosphonic acid group-containing (meth)acrylate-based monomer is 6-methacryloxyhexyl-phosphonoacetate or 6-methacryloxyhexyl-3-phosphonopropionate.
• a blending ratio of (b) the acidic group-containing polymerizable monomer may appropriately vary depending on the use purpose of the composition, and is adjusted in the range of 1.0 to 20.0 parts by weight, preferably is adjusted in the range of 4.0 to 15.5 parts by weight based on 100 parts by weight of (a) the silane coupling agent.
• the volatile organic solvent in the present invention is methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, and isopropyl ether, as well as a radical-polymerizable monomer such as (meth)acrylic acid ester, (meth)acrylamide, vinyl ester and the like.
• ethanol Preferable is ethanol, and acetone, and a blending ratio of (c) the volatile organic solvent may appropriately vary depending on the use purpose of the composition, and is adjusted in the range of 28 to 99 parts by weight, preferably is adjusted in the range of 42.25 to 94.8 parts by weight.
• the dental adhesive composition of the present invention contains, as an essential component, (a) the silane coupling agent, (b) the acidic group-containing polymerizable monomer, and (c) the volatile organic solvent, other components may be selected and added appropriately thereto, and addition components, that is, a radical polymerizable monomer, a photopolymerization initiator, a photopolymerization promoter, a thermal polymerization initiator, a polymerization catalyst, an inorganic and organic filler, a polymerization inhibitor, and a pigment may be appropriately incorporated therein, depending on the utility.
• addition components that is, a radical polymerizable monomer, a photopolymerization initiator, a photopolymerization promoter, a thermal polymerization initiator, a polymerization catalyst, an inorganic and organic filler, a polymerization inhibitor, and a pigment may be appropriately incorporated therein, depending on the utility.
• the radical polymerizable monomer can be added to the dental adhesive composition of the present invention.
• examples of the radical polymerizable monomer include (meth)acrylates such as (meth)acrylic acid, methyl (meth)acrylate, and ethyl(meth)acrylate, and (meth)acrylates having an alkyl side chain substituted with a hydroxy group and a halogen, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,2′-bis ⁇ 4-(meth)acryl
• radical polymerizable monomers are used alone, or by appropriately combining them and, inter alia, a combination of bisphenol A diglycidyl(meth)acrylate of a polymerizable monomer such as di(meth)acrylate and the like, and triethylene glycol di(meth)acrylate is preferable.
• the known compounds which are generally used in dental compositions are used without any limitation.
• the polymerization initiator is generally classified into a thermal polymerization initiator and a photopolymerization initiator.
• a photosensitizer generating a radical by light irradiation can be used.
• the photosensitizer for ultraviolet ray include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether and the like, benzophenone-based compounds such as acetoin benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and the like, and thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.
• a photosensitizer which initiates polymerization with visible light does not need ultraviolet-ray which is harmful to a human body, it is suitably used.
• a-diketones such as benzil, camphorquinone, a-naphthil, acetonaphthene, p,p′-dimethoxybenzil, dichlorobenzylacetil, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone and the like.
• camphorquinone is used.
• a combination of the photosensitizer with a photopolymerization promoter it is also preferable to use a combination of the photosensitizer with a photopolymerization promoter.
• a photopolymerization promoter it is more preferable to use a compound in which an aromatic group is directly substituted with a nitrogen atom.
• tertiary amines such as N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic acid methyl ester, N,N-diary amines such as N,N-
• oxycarboxylic acids such as citric acid, malic acid, tartaric acid, glycolic acid, glucuronic acid, a-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, dimethylolpropionic acid and the like.
• organic peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate and the like, and azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, azobiscyanovaleric acid and the like are suitably used.
• polymerization may be performed at a normal temperature.
• the amine compound secondary or tertiary amines in which an amine group is bound to an aryl group are more preferably used from a viewpoint of curing promotion.
• N,N-dimethyl-p-toluidine, N,N-dimethylaniline, N,N- ⁇ -hydroxyethyl-aniline, N,N-di( ⁇ -hydroxyethyl)-aniline, N,N-di( ⁇ -hydroxyethyl)-p-toluidine, N-methyl-aniline, and N-methyl-p-toluidine are preferable.
• sulfinic acid salts include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like.
• borate examples include a sodium salt, a lithium salt, a potassium salt, a magnesium salt, a tetrabutylammonium salt, and a tetramethylammonium salt of trialkylphenylboron, trialkyl(p-fluorophenyl)boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group etc.).
• organic boron compounds such as tributylborane, tributylborane partial oxides and the like which generate a radical by a reaction with oxygen or water may be used as an organic metal-type polymerization initiator.
• the known various additives may be blended into the dental adhesive composition of the present invention as necessary.
• examples of such the additives include a polymerization inhibitor, a coloring agent, a discoloration preventing agent, a fluorescent agent, a ultraviolet absorbing agent, an antibacterial agent and the like.
• the inorganic and organic fillers include organic fillers obtained by grinding an organic polymer powder of polymethyl methacrylate, polyethyl methacrylate, a copolymer of methyl methacrylate and ethyl methacrylate, polystyrene and the like, or a cured product of a thermosetting resin, or a cured product of a thermosetting resin containing an inorganic filler, and inorganic fillers (kaolin, talc, quartz, silica, colloidal silica, alumina, aluminosilicate, silicon nitride, barium sulfate, calcium phosphate, barium sulfate, glass powder etc.), and composite fillers of an inorganic filler and an organic filler, and they are suitable for the composition to use as a powder/liquid type, a paste or a slurry. A surface of them may be covered with a coupling agent containing a silanol group ( ⁇ -methacryloxypropyl)
• polymerization retarder examples include hydroquinone, hydroquinone monomethyl ester, butylated hydroxytoluene and the like, and is suitable for stabilizing a shelf life of the composition.
• Bis-GMA Bisphenol A diglycidyl methacrylate
• R-972 Fine particle silicic acid [manufactured by Japan Aerosil Co., Ltd.]
• Aluminum oxide plate about 15 ⁇ 15 ⁇ 2 mm [manufactured by Japan Fine Ceramics Co., Ltd.]
• Zirconium oxide plate about 15 ⁇ 15 ⁇ 2 mm [manufactured by Japan Fine Ceramics Co., Ltd.]
• Porcelain disk-like plate diameter 15.0 ⁇ 5.0 mm [porcelain for baking dental metal [trade name “Vintage Hello” (manufactured by Shofu)]]
• a dental ceramics material consisting of aluminum oxide or a zirconium oxide
• employing an aluminum oxide plate about 15 ⁇ 15 ⁇ 2 mm [manufactured by Japan Fine Ceramics Co., Ltd.]
• a zirconium oxide plate about 15 ⁇ 15 ⁇ 2 mm [manufactured by Japan Fine Ceramics Co., Ltd.]
• An adhesive composition was prepared by mixing at a weight ratio shown in Tables 1 to 3.
• a flat surface of an aluminum oxide or zirconium oxide plate of about 15 ⁇ 15 ⁇ 2 mm was polished with a No. 240, then, No. 600 silicon carbide paper [manufactured by Sankyo Rigaku Co., Ltd.] under running water to obtain a smooth surface, the smooth surface was subjected to air ablation (50 ⁇ m alumina beads, 2.5 kgf/cm 2 pressure), and ultrasound-washed and air-dried to obtain an adherend.
• An adhesive composition was coated on an adhesive surface of the adherend with a mini-brush, this was as it was allowed to stand for 30 seconds; and dried with an air syringe to such an extent that fluidity of the adhesive composition disappeared.
• an adhesive surface of a cylindrical stainless bar of diameter 5 mm ⁇ height 10 mm was subjected to air ablation (50 ⁇ m alumina beads, 5 kgf/cm 2 pressure) and, thereafter, the surface was ultrasound-washed and air-dried to obtain a jig for measuring an adhesion strength.
• Adhesion was performed while “IMPERVA DUAL” which had been uniformly kneaded into a paste intervened between an adhesive surface of the adherend and an adhesive surface of a stainless bar. Thereupon, an extra cement was removed with a mini-brush, and photopolymerization was performed for 10 seconds using “Shofu Grip Light II” in a cement margin. All seven test pieces were immersed in water at 37° C.
• a tensile adhesion strength was measured.
• a tensile adhesion strength was measured using a universal tester (manufactured by Instron) under the condition of a cross-head speed of 1 mm/min. All adhesion tests were performed at room temperature of 23° C. ⁇ 1° C.
• a tensile adhesion strength when an adhesive composition was prepared by blending and mixing at a weight ratio shown in Tables 1 to 4, and this was brought into the sealed state, and was used under storage environment at 23° C. within 24 hours was adopted as an “initial” tensile adhesion strength.
• a tensile adhesion strength when an adhesive composition was prepared by blending and mixing at a weight ratio shown in Tables 1 to 4, and this was brought into the sealed state, and was used after storage for 2 months under storage environment at 50° C. was adopted as tensile strength “after 50° C. 2 months storage”.
• a porcelain for baking a dental metal [trade name “Vintage Hello” (manufactured by Shofu)] was employed, and a disk-like (diameter 15.0 ⁇ 5.0 mm) fired product was prepared using a vacuum electric furnace for firing a porcelain [trade name “Twin Mat” (manufactured by Shofu)], and a tensile adhesion strength test was performed.
• An adhesive composition was prepared by mixing at a weight ratio shown in Tables 1 to 3.
• a flat surface of a disk-like (diameter 15.0 ⁇ 5.0 mm) fired product was polished under running water using a No. 240, then, No. 600 silicon carbide paper [manufactured by Sankyo Rigaku Co., Ltd.] to obtain a smooth surface, and this was ultrasound-washed and air-dried to obtain an adherend.
• An adhesive composition was coated on an adhesive surface of the adherend with a mini-brush, and this was as it was allowed, to stand for 30 seconds, and dried with an air syringe to such an extent that fluidity of the adhesive composition disappeared.
• an adhesive surface of a cylindrical Cobaltan (cobalt chromium alloy: manufactured by Shofu) bar of diameter 5 mm ⁇ height 10 mm was subjected to air ablation (50 ⁇ m alumina beads, 5 kgf/cm 2 pressure) and, thereafter, was ultrasound-washed and air-dried to obtain a jig for measuring an adhesion strength.
• Adhesion was performed while “IMPERVA DUAL” which had been uniformly kneaded into a paste intervened between an adhesive surface of an adherend and an adhesive surface of a stainless bar. Thereupon, an extra cement was removed with a mini-brush, and photopolymerization was performed for 10 seconds using “Shofu Grip Light II” in a cement margin.
• test pieces were immersed in water at 37° C. and, after immersion in water at 37° C. for 24 hours, a tensile adhesion strength was measured.
• a tensile adhesion strength was measured using a universal tester (manufactured by Instron) under the condition of a cross-head speed of 1 mm/min. All adhesion tests were performed at room temperature of 23° C. ⁇ 1° C.
• a tensile adhesion strength when an adhesive composition was prepared by blending and mixing at a weight ratio shown in Tables 1 to 4, and this was brought into the sealed state, and was used under storage environment at 23° C. within 24 hours was adopted as an “initial” tensile adhesion strength.
• a tensile adhesion strength when an adhesive composition was prepared by blending and mixing at a weight ratio shown in Tables 1 to 4, and this was brought into the sealed state, and was used after storage for 2 months under storage environment at 50° C. was adopted as tensile strength “after 50° C. 2 months storage”.
• a blending amount of (a) the silane coupling agent was set to be 40 parts by weight, and a blending amount of (b) the acidic group-containing polymerizable monomer varied, in the adhesive compositions and, as apparent in comparison between Comparative Example 1 and Examples 1 to 5, adhesion with a porcelain, or alumina or zirconia is dramatically improved by the effect of blending (b) the acidic group-containing polymerizable monomer.
• adhesion with a porcelain, or alumina or zirconia of the adhesive composition in which a blending amount of (b) the acidic group-containing polymerizable monomer based on 100 parts by weight of (a) the silane coupling agent is adjusted in the range of 1.6 to 18.6 parts by weight is dramatically improved as compared with adhesion of a composition in which no (b) acidic group-containing polymerizable monomer is blended, and storage stability when formulated into a one-component composition is also better.
• Examples 16 to 20 are an adhesive composition containing a radical polymerizable monomer and a photopolymerization initiator in the composition, and adhesion with a porcelain, or alumina or zirconia of an adhesive composition in which a blending amount of (b) the acidic group-containing polymerizable monomer based on 100 parts by weight of (a) the silane coupling agent is adjusted in the range of 1.6 to 18.6 parts by weight is better, and storage stability when formulated into a one-component composition is also better.
• one-component dental adhesive composition which can exhibit excellent adhesion and durability on any material of a dental ceramics, and an organic composite containing an inorganic compound, and is excellent in can-stability can be provided.

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• 2007
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