WO2015064090A1 - 歯科用色調調整材キット - Google Patents
歯科用色調調整材キット Download PDFInfo
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- WO2015064090A1 WO2015064090A1 PCT/JP2014/005452 JP2014005452W WO2015064090A1 WO 2015064090 A1 WO2015064090 A1 WO 2015064090A1 JP 2014005452 W JP2014005452 W JP 2014005452W WO 2015064090 A1 WO2015064090 A1 WO 2015064090A1
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Classifications
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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
- A61K6/64—Thermal radical initiators
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C5/00—Filling or capping teeth
- A61C5/70—Tooth crowns; Making thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C5/00—Filling or capping teeth
- A61C5/70—Tooth crowns; Making thereof
- A61C5/77—Methods or devices for making crowns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/40—Primers
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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
- A61K6/62—Photochemical radical initiators
-
- 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
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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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/816—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising titanium oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a dental color adjustment material kit, and more particularly to a dental color adjustment material kit suitable for color adjustment of a dental restoration material.
- a restoration material of a crown using a sintered zirconia block, a glass block, or a resin block processed using CAD / CAM is frequently used to repair a tooth defect portion damaged by caries or the like. Since the zirconia sintered body is white, the crown restoration material formed of the zirconia sintered body is inferior in aesthetics as compared with natural teeth.
- the zirconia sintered body block, the glass block, and the resin block can be colored, but in order to adjust to a desired color tone, various kinds of colorants having different color tones are required. It is also possible to use a multi-layer block to reproduce the color tone of the natural tooth, but it is difficult to completely reproduce the color tone of the natural tooth. Therefore, further studies have been conducted on the method of adjusting the color tone of the surface of these crown restorative materials.
- Patent Document 1 a matrix monomer composed of bisphenol-A-diglycidyl acrylate, urethane dimethacrylate and triethylene glycol dimethacrylate, quartz, metal oxide, a filler mixture composed of dental glass, an initiator, a small amount of dental
- a method for correcting the color of a denture or tooth surface by applying a photocurable correction color characterized by having a pigment for use, and a color kit for color correction have been proposed.
- Patent Document 2 acidic group-containing polymerizable monomer (a), water (b) and water are used mainly for the purpose of preventing tooth coloring and discoloration, in particular, tooth coloring and bleaching after bleaching.
- a surface composition comprising a primer composition comprising a water-soluble solvent (c), a polyfunctional polymerizable monomer (f), a volatile solvent (g) and a photopolymerization initiator (h).
- a dental coating kit having an adhesive composition and excellent adhesion to teeth has been proposed.
- Patent Document 2 since the surface hardening property of the correction color proposed in Patent Document 1 is low, the denture or tooth surface to which the correction color is applied is easily colored with coffee or the like immediately after application, and the glossiness is easy. To drop. On the other hand, in Patent Document 2, since the focus was on making the teeth look whiter and beautiful, the color tone of the tooth after restoration was different from the color tone of the natural tooth. In Patent Document 2, the main use is for teeth. When the primer and the surface lubricant composition described in the Examples of Patent Document 2 are applied to a crown restoration material, the surface lubricant composition of The surface drying property was not sufficient.
- the present invention improves the surface drying property of the dental color adjusting material, hardly causes discoloration due to coffee or the like of the dental color adjusting material after curing, improves the wear resistance, and has a thin coating thickness. It is another object of the present invention to provide a dental color tone adjusting material kit that can be adjusted to a desired color tone.
- a dental color adjustment material kit comprising a primer composition (A) and a dental color adjustment material (B),
- the primer composition (A) contains an acidic group-containing polymerizable monomer (a) and a volatile organic solvent (b)
- the dental color tone adjusting material (B) contains a polymerizable monomer (d), a polymerization initiator (e), agglomerated particles (f), titanium dioxide (g) and a pigment (h),
- the content of the acidic group-containing polymerizable monomer (a) is in the range of 0.05 to 45% by weight of the total weight of the primer composition (A)
- the content of the volatile organic solvent (b) is in the range of 55 to 99.95% by weight of the total weight of the primer composition (A)
- the polymerizable monomer (d) contains a polyfunctional acrylate monomer (d1) having three or more acryloyl groups in one molecule and a volatile monofunctional (meth) acrylate monomer (d2).
- the total amount of the monomer (d1) and the monomer (d2) is 88% by weight or more based on the weight of the polymerizable monomer (d),
- the agglomerated particles (f) are chain agglomerated particles of ultrafine filler having an average primary particle diameter of 1 to 50 nm,
- the content of the agglomerated particles (f) is in the range of 5 to 20 parts by weight with respect to 100 parts by weight of the total weight of the polymerizable monomer (d) and the agglomerated particles (f).
- the titanium dioxide (g) content is in the range of 0.05 to 2 parts by weight with respect to 100 parts by weight as the total weight of the polymerizable monomer (d) and the agglomerated particles (f).
- the pigment (h) is a pigment excluding the titanium dioxide (g). The above object was achieved by the dental color tone adjusting material kit.
- the surface dryness is good, the color tone adjustment material after curing is less likely to be discolored by coffee or the like, the wear resistance is improved, and the desired color tone is achieved even when the coating thickness is thin. It is possible to provide a dental color adjustment material kit that can be adjusted.
- the dental color adjusting material kit of the present invention includes a primer composition (A) and a dental color adjusting material (B).
- the dental color tone adjusting material kit of the present invention comprises a primer composition (A) and a dental color tone adjusting material (B).
- the primer composition (A) contains an acidic group-containing polymerizable monomer (a) and a volatile organic solvent (b).
- the content of the acidic group-containing polymerizable monomer (a) is in the range of 0.05 to 45% by weight with respect to the total weight of the primer composition (A), and the content of the volatile organic solvent (b). Is in the range of 55 to 99.95% by weight of the total weight of the primer composition (A).
- the dental color tone adjusting material (B) is composed of a polymerizable monomer (d), a polymerization initiator (e), a chain aggregated particle (f) of ultrafine filler having an average primary particle diameter of 1 to 50 nm, Contains titanium dioxide (g) and pigment (h).
- the polymerizable monomer (d) is composed of a polyfunctional acrylate monomer (d1) having three or more acryloyl groups in one molecule and a volatile monofunctional (meth) acrylate monomer (d2). It is contained in an amount of 88% by weight or more based on the weight of the monomer (d).
- the dental color tone-adjusting material (B) is composed of a chain agglomeration of ultrafine filler with respect to a total weight of 100 parts by weight of the polymerized monomer (d) and the chain agglomerated particles (f) of the ultrafine filler. 5 to 20 parts by weight of particles (f) and 0.05 to 2 parts by weight of titanium dioxide (g) are contained.
- the primer composition (A) is intended to be used before using the dental color adjusting material (B).
- adhesion between the dental color tone adjusting material (B) and an adherend such as a dental restorative material such as a tooth or crown restorative material, particularly a dental restorative material can be obtained. improves.
- a dental restorative material such as a tooth or crown restorative material
- Acidic group-containing polymerizable monomer (a) The acidic group-containing polymerizable monomer (a) contained in the primer composition (A) has a polymerizable structure, and forms a cured product by polymerization. Moreover, the adhesiveness with respect to the adherend surface of a primer composition (A) improves by using an acidic group containing polymeric monomer (a).
- the acidic group-containing polymerizable monomer (a) has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and further acryloyl.
- a polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, a vinyl group, and a styrene group.
- a polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, a vinyl group, and a styrene group.
- Specific examples of the acidic group-containing polymerizable monomer (a) are given below.
- Phosphoric acid group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrophosphate Genphosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyl Oxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide dec
- Examples of the pyrophosphate group-containing polymerizable monomer include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meth) acryloyl pyrophosphate.
- Examples thereof include oxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and ammonium salts thereof.
- Examples of the thiophosphate group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- (meth) acryloyloxybutyldihydro Genthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- (meta ) Acryloyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydrogen Phosphate, 11- (meth) acryloyloxyundecyl dihydrogen thio
- Examples of the phosphonic acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxyhexyl-3.
- -Phosphonopropionate 10- (meth) acryloyloxydecyl-3-phosphonopropionate
- Illustrative are phosphonoacetates and their acid chlorides, alkali metal salts and ammonium salts.
- Examples of the sulfonic acid group-containing polymerizable monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth) acrylate.
- Examples of the carboxylic acid group-containing polymerizable monomer include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.
- Examples of the polymerizable monomer having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 2-
- Examples of the polymerizable monomer having a plurality of carboxyl groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 10 -(Meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 13- ( (Meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxybutyl trimellitate Tate, 4- (meth) acrylo
- acidic group-containing polymerizable monomers phosphoric acid groups or pyrophosphoric acid group-containing (meth) acrylic monomers are preferable because they exhibit better adhesion to adherends.
- Acid group-containing (meth) acrylic monomers are preferred.
- a divalent phosphate group-containing (meth) acrylic monomer having an alkyl group or alkylene group having 6 to 20 carbon atoms as the main chain in the molecule is more preferable, and the number of carbon atoms as the main chain in the molecule.
- the acidic group-containing polymerizable monomer (a) may be used alone or in combination of two or more.
- the blending amount of the acidic group-containing polymerizable monomer (a) is too much or too little, the adhesive force to the adherend surface may be lowered.
- the blending amount is excessive, a large amount of the acidic group-containing polymerizable monomer (a) remains on the adherend, and as a result, the surface dryness of the dental color tone adjusting material decreases, Coloring resistance or lubrication durability of the dental color tone adjusting material may be lowered.
- the content of the acidic group-containing polymerizable monomer (a) in the primer composition (A) is in the range of 0.05 to 45% by weight with respect to the total weight of the primer composition (A), 0.05 to 40% by weight is preferable, 0.1 to 20% by weight is more preferable, and 0.5 to 10% by weight is particularly preferable.
- the volatile organic solvent (b) means an organic solvent having a boiling point of 120 ° C. or less at normal pressure and in a liquid state at 25 ° C. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-propanol, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, diisopropyl ether, hexane, toluene, chloroform, ethyl acetate, methyl acrylate , Methyl methacrylate, ethyl methacrylate and the like.
- ethanol, 2-propanol, 2-methyl-2-propanol, acetone, and methyl methacrylate are preferable in view of safety and volatility.
- the compound applicable to both acidic group containing polymeric monomer (a) and volatile organic solvent (b) shall correspond to acidic group containing polymeric monomer (a).
- the content of the volatile organic solvent (b) is based on the total weight of the primer composition (A) from the viewpoint of the surface drying property of the dental color adjusting material (B) used in combination with the primer composition (A). It is in the range of 55 to 99.95% by weight, preferably 75 to 99.9% by weight, more preferably 80 to 99.9% by weight, still more preferably 85 to 99.5% by weight, and 90 to 99.5% by weight. % Is particularly preferred.
- the primer composition (A) can further contain a silane coupling agent (c).
- the silane coupling agent (c) improves the adhesion effect between the primer composition (A) and the adherend by dehydration condensation with the silanol group of the adherend.
- a known silane coupling agent can be used without any limitation.
- 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3-aminopropyltri Ethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane and hydrolysates thereof are preferred.
- the silane coupling agent (c) may be used alone or in combination of two or more.
- the primer composition (A) is, for example, acidic group-containing polymerizable monomer (a): 0.05 to 40% by weight, volatile organic solvent (b): 55 to 99.9% by weight, silane coupling agent (c): 0.0. 01 to 40% by weight is preferable.
- silane coupling agent ( c): 0.1 to 10% by weight is more preferable.
- the content of the silane coupling agent (c) may be 0.5 to 10% by weight based on the total weight of the primer composition (A).
- the primer composition (A) may further contain a polymerizable monomer having no acidic group, water, a polymerization initiator, an oxidizing agent, a reducing agent, a filler and the like as long as the effects of the invention are not impaired.
- the polymerizable monomer having no acidic group does not include a material corresponding to the acidic group-containing polymerizable monomer (a), the volatile organic material (b), or the silane coupling agent (c).
- the water remaining on the adherend surface may reduce the surface drying property of the dental color tone adjusting material, which may deteriorate the color resistance and lubrication durability. It is preferable that a thing (A) does not contain water.
- the dental color adjusting material (B) is intended to be used after the use of the primer composition (A).
- the surface dryness of the dental color tone adjusting material (B) is improved, and the dental color tone adjusting material after curing is less likely to be discolored, and is resistant to coloring and abrasion. Will improve.
- Polymerizable monomer (d) The polymerizable monomer (d) contained in the dental color tone adjusting material (B) is composed of a polyfunctional acrylate monomer (d1) having three or more acryloyl groups in one molecule and a volatile monofunctional (meth). An acrylate monomer (d2) is included. The total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2) is 88% by weight or more based on the total weight of the polymerizable monomer (d). .
- the total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2) is a polymerizable single amount. 94 weight% or more is preferable with respect to the total weight of a body (d), and 98 weight% or more is more preferable. More preferably, the polymerizable monomer (d) consists only of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2).
- the polyfunctional acrylate monomer (d1) has three or more acryloyl groups in one molecule.
- Examples of the polyfunctional acrylate monomer (d1) include trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 2, Examples include 2,6,6-tetrakis (acryloyloxymethyl) -4-oxaheptane-1,7-diol 1-acrylate.
- pentaerythritol triacrylate and dipentaerythritol hexaacrylate are preferable from the viewpoints of handleability and safety.
- the polyfunctional acrylate monomer (d1) may be used alone or in combination of two or more.
- the content of the polyfunctional acrylate monomer (d1) is 10 with respect to 100 parts by weight of the total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2). It is preferably in the range of 80 parts by weight.
- the content of the polyfunctional acrylate monomer (d1) is less than 10 parts by weight, the surface drying property of the dental color tone adjusting material (B) decreases, and the color resistance of the dental color tone adjusting material after curing or Lubrication durability may be reduced.
- the content of the polyfunctional acrylate monomer (d1) exceeds 80 parts by weight, the operability of the dental color tone adjusting material (B) is deteriorated, and it may be difficult to apply to the adherend surface.
- the content of the polyfunctional acrylate monomer (d1) is 30 with respect to 100 parts by weight of the total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2). More preferred is 75 to 75 parts by weight, and still more preferred is 50 to 70 parts by weight.
- the volatile monofunctional (meth) acrylate monomer (d2) means a monofunctional (meth) acrylate monomer that has a boiling point of 120 ° C. or less at normal pressure and is liquid at 25 ° C.
- Examples of the volatile monofunctional (meth) acrylate monomer (d2) include methyl (meth) acrylate and ethyl (meth) acrylate. Methyl methacrylate is most preferable from the viewpoint of low toxicity and low boiling point.
- the volatile monofunctional (meth) acrylate monomer (d2) may be used alone or in combination of two or more.
- the volatile monofunctional (meth) acrylate monomer (d2) is 100 parts by weight of the total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2). It is preferably in the range of 20 to 90 parts by weight.
- the content of the volatile monofunctional (meth) acrylate monomer (d2) is less than 20 parts by weight, the operability of the dental color adjusting material (B) is deteriorated, and it is difficult to apply it on the adherend surface. There is.
- the blending amount of the volatile monofunctional (meth) acrylate monomer (d2) exceeds 90 parts by weight, the surface dryness of the dental color adjusting material is lowered, and the resistance of the dental color adjusting material after curing is reduced. Coloring or lubrication durability may be reduced.
- the content of the volatile monofunctional (meth) acrylate monomer (d2) is 100 parts by weight of the total amount of the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2). On the other hand, the amount is more preferably 25 to 70 parts by weight, still more preferably 30 to 50 parts by weight.
- the polymerizable monomer (d) blended in the dental color tone adjusting material (B) is a polymerizable monomer other than the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2).
- a monomer (d3) may be contained.
- the polymerizable monomer (d3) a known polymerizable monomer used in a dental composition is used without any limitation.
- Specific examples of the polymerizable monomer (d3) include esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid.
- (I) monofunctional (meth) acrylate and monofunctional (meth) acrylamide isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meta) ) Acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, (meth) acryloylo Examples thereof include xi
- the polymerizable monomer (d3) one type may be blended, or a plurality of types may be blended.
- the compounding amount of the polymerizable monomer (d3) is excessive, the surface drying property of the dental color tone adjusting material (B) may be lowered.
- the surface drying property of the dental color tone adjusting material (B) is lowered, the coloring resistance or the lubrication durability of the dental color tone adjusting material (B) after curing may be lowered. Therefore, it is most preferable that the polymerizable monomer (d3) is not contained in the polymerizable monomer (d), but when it is contained, the content is the total weight of the polymerizable monomer (d). On the other hand, it is preferably 12% by weight or less, more preferably 6% by weight or less, and further preferably 2% by weight or less.
- Polymerization initiator (e) The polymerization initiator (e) contained in the dental color tone adjusting material (B) can be selected from generally used polymerization initiators, and is particularly preferably a polymerization initiator used for dental use. Used. Especially, the polymerization initiator of photopolymerization or chemical polymerization can be used individually or in combination of 2 or more types as appropriate.
- photopolymerization initiator examples include (bis) acylphosphine oxides and ⁇ -diketones.
- Examples of (bis) acylphosphine oxides used as the photopolymerization initiator include acylphosphine oxides and bisacylphosphine oxides.
- Acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine Examples include oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, and salts thereof.
- bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, 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 5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide, and salts thereof.
- Examples of the ⁇ -diketone used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′- Examples thereof include oxybenzyl and acenaphthenequinone.
- camphorquinone is preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.
- photopolymerization initiators 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2 It is preferable to use at least one selected from the group consisting of 1,4,6-trimethylbenzoylphenylphosphine oxide sodium salt and camphorquinone.
- the composition has excellent photocurability in the visible and near-ultraviolet region, and exhibits sufficient photocurability even when using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp. Is obtained.
- an organic peroxide is preferably used as the chemical polymerization initiator.
- the organic peroxide used for a chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.
- ketone peroxide examples include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.
- hydroperoxide examples include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.
- diacyl peroxide examples include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. Can be mentioned.
- Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Examples thereof include bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne.
- Peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t- And butyl peroxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester.
- Peroxyesters include ⁇ -cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate.
- t-amylperoxy-2-ethylhexanoate t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate
- examples thereof include t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid.
- peroxydicarbonate examples include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n -Propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate and the like.
- diacyl peroxide is preferably used, and among them, benzoyl peroxide is more preferably used from the comprehensive balance of safety, storage stability, and radical generating ability.
- the content of the polymerization initiator (e) is not particularly limited, but from the viewpoint of drying property and the like of the obtained dental color tone adjusting material (B), the polymerization is performed with respect to 100 parts by weight of the polymerizable monomer (d). It is preferable that 0.001 to 30 parts by weight of the initiator (e) is contained. When the content of the polymerization initiator is less than 0.001 part by weight, the polymerization reaction of the polymerizable monomer (d) does not proceed sufficiently, and the mechanical strength and / or adhesion of the dental color tone adjusting material after curing. It may cause a decrease in power.
- the content of the polymerization initiator (e) is more preferably 0.05 parts by weight or more, and still more preferably 0.10 parts by weight or more with respect to 100 parts by weight of the polymerizable monomer (d).
- the content of the polymerization initiator exceeds 30 parts by weight, it may be precipitated from the dental color tone adjusting material (B), so it is more preferably 20 parts by weight or less, and even more preferably 15 parts by weight. Part or less, more preferably 10 parts by weight or less.
- the dental color adjusting material (B) may further contain a polymerization accelerator.
- the polymerization accelerator include amines, sulfinic acid, and salts thereof, aldehydes, and thiol compounds.
- Amines are divided into aliphatic amines and aromatic amines.
- the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N, N-dimethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyl Diethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethanolamine Butylamine, tertiary aliphatic
- tertiary aliphatic amines are preferable from the viewpoint of drying property and storage stability of the dental color tone adjusting material (B).
- N, N-dimethylaminoethyl methacrylate, N-methyldiethanolamine and triethanol are preferred.
- An amine is more preferably used.
- aromatic amine examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and 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-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl
- N, N-di (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzoic acid from the viewpoint of improving the surface drying property of the dental color tone adjusting material (B).
- At least one selected from the group consisting of ethyl, n-butoxyethyl N, N-dimethylaminobenzoate and 4-N, N-dimethylaminobenzophenone is preferably used.
- 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.
- aldehydes include terephthalaldehyde and benzaldehyde derivatives.
- the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.
- pn-octyloxybenzaldehyde is preferably used from the viewpoint of improving the surface drying property of the dental color tone adjusting material (B).
- thiol compound examples include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.
- a polymerization accelerator is 0 with respect to 100 weight part of polymerizable monomers (d). It is preferably 0.001 to 30 parts by weight. When the content of the polymerization accelerator is less than 0.001 part by weight, the polymerization does not proceed sufficiently, leading to a decrease in the mechanical strength and / or adhesive strength of the dental color tone adjusting material (B) after curing. More preferably 0.05 parts by weight or more, and even more preferably 0.1 parts by weight or more.
- the content of the polymerization accelerator exceeds 30 parts by weight, it may be precipitated from the dental color tone adjusting material (B), so that it is more preferably 20 parts by weight or less, and even more preferably 10 parts by weight. It is as follows.
- the chain-shaped agglomerated particles (f) of the ultrafine particle filler contained in the dental color adjusting material (B) improve the surface hardness of the dental color adjusting material (B) and have excellent lubrication durability.
- the dental color tone adjusting material (B) is provided with thixotropy, has a function of adjusting the viscosity to be easily applied, and has an effect of inhibiting the precipitation of the pigment (h) to be blended at the same time.
- the chain aggregated particles (f) of the ultrafine filler are those having an average primary particle diameter of 1 to 50 nm from the viewpoint of surface smoothness of the dental color tone adjusting material (B) after curing.
- the average particle size of the ultrafine particle filler is the number of particles (200 particles) observed in a unit field of view of a scanning electron microscope (Hitachi, S-4000 type) photograph of ultrafine particles.
- the particle diameter can be determined by measuring the particle size using image analysis type particle size distribution software (Macview (Mounttech)). At this time, the particle diameter of the particle is obtained as a circle equivalent diameter which is the diameter of a circle having the same area as the particle, and the average primary particle diameter is calculated from the number of particles and the particle diameter.
- the type and shape are not particularly limited, and chain-shaped agglomerated particles of known ultrafine particle fillers can be used.
- the chain aggregate particles of hydrophilic ultrafine particle filler and the chain aggregate particles of hydrophobic ultrafine particle filler may be used in combination.
- the ultrafine particle filler that exists in a monodispersed state without agglomerating primary particles cannot be adjusted in viscosity even when blended with the dental color tone adjusting material (B), and the sedimentation of the pigment cannot be suppressed. For this reason, color unevenness is likely to occur, which is not preferable.
- chain-like agglomerated particles of hydrophilic ultrafine filler manufactured by Nippon Aerosil Co., Ltd., trade names: “AEROSIL (registered trademark) 130”, “AEROSIL (registered trademark) 380”, “AEROSIL (registered trademark) OX50”, “AEROXIDE (registered trademark) AluC”, “AEROXIDE (registered trademark) TiO 2 P25”, “AEROXIDE (registered trademark) TiO 2 P25S”, “VP Zirconium Oxide 3-YSZ”, “VP Zirconium Oxide PH” are preferably used. It is done.
- the chain agglomerate particles of the hydrophobic ultrafine particle filler include those obtained by subjecting a hydrophilic filler to a surface treatment with a silane coupling agent or the like in advance.
- Examples of the silane coupling agent used for the surface treatment of the chain-like agglomerated particles of the hydrophobic ultrafine particle filler include the same silane coupling agents (c) used in the primer composition (A).
- Examples of the agglomerated particles of ultrafine fillers that have been previously hydrophobized include, for example, “AEROSIL (registered trademark) R972”, “AEROSIL (registered trademark) R974” manufactured by Nippon Aerosil Co., Ltd. It is done.
- the chain-like agglomerated particles of the hydrophilic ultrafine particle filler may be surface-treated with a silane coupling agent or the like to be used as a hydrophobic ultrafine particle filler.
- a surface treatment can be performed by dispersing chain aggregate particles of hydrophilic ultrafine particle filler in water, adding 3-methacryloyloxypropyltrimethoxysilane, and then distilling off the solvent under reduced pressure and drying. it can.
- chain-like agglomerated particles of the hydrophilic ultrafine particle filler product names “AEROSIL (registered trademark) Ar380”, “AEROSIL (registered trademark) OX50”, “AEROXIDE (registered trademark) Alu C” manufactured by Nippon Aerosil Co., Ltd. And so on.
- the content of the chain agglomerated particles (f) of the ultrafine particle filler is 100 parts by weight with respect to the total amount of the polymerizable monomer (d) and the chain agglomerated particles (f) of the ultrafine particle filler. 5 to 20 parts by weight, preferably 7 to 18 parts by weight, and more preferably 9 to 16 parts by weight. If the content of the agglomerated particles (f) is too small, not only the viscosity of the dental color tone adjusting material (B) becomes too low, the operability is lowered, but also the pigment settles during storage, resulting in color unevenness. Sometimes. In addition, the mechanical strength of the dental color tone adjusting material may decrease, and the wear resistance in the oral cavity may decrease.
- the dental color tone adjusting material (B) becomes too viscous, not only the operability is lowered but also the dental color tone adjusting material may not be applied thinly.
- the thickness of the dental color adjustment material increases, the shape of the dental restorative material produced in consideration of occlusion may be affected, and readjustment may be necessary.
- the dental color tone-adjusting material (B) containing chain aggregate particles (f) of the ultrafine particle filler has a viscosity at 23 ° C. of 20 to 20 so as to realize appropriate operability and to be applied thinly.
- a range of 500 mPa ⁇ s is preferred, a range of 20 to 200 mPa ⁇ s is more preferred, a range of 20 to 100 mPa ⁇ s is still more preferred, and a range of 20 to 70 mPa ⁇ s is particularly preferred.
- the viscosity of the dental color tone adjusting material (B) can be measured by the method described in the Examples section.
- a dental color tone-adjusting material (B) having the above-mentioned preferable viscosity by simply dispersing the chain-like agglomerated particles (f) of the ultrafine particle filler in the polymerizable monomer (d).
- a high shearing force is applied when the chain aggregated particles (f) of the ultrafine particle filler are dispersed in the polymerizable monomer (d). It is preferable to disperse the agglomerated particles (f) of the ultrafine filler in the composition in a state of being crushed to some extent.
- the polyfunctional acrylate monomer (d1) and the chain aggregated particles (f) of the ultrafine particle filler are kneaded in advance using a kneader while applying a high shearing force
- a method of mixing a composition in which a polymerization initiator (e), a pigment (h), and titanium dioxide (g) are dissolved and dispersed can be considered. Since the polyfunctional acrylate monomer (d1) has a high viscosity, the polyfunctional acrylate monomer (d1) and the chain aggregated particles (f) of the ultrafine particle filler are kneaded while applying a high shearing force.
- the chain-like agglomerated particles (f) of the ultrafine particle filler are dispersed in the composition in a state of being crushed to some extent.
- the kneading time of the polyfunctional acrylate monomer (d1) and the chain aggregated particles (f) of the ultrafine particle filler is not particularly limited, but is preferably about 0.1 to 10 hours, preferably about 1 to 10 hours. More preferred.
- the kneading temperature is not particularly limited, but may be heated during kneading. The kneading temperature is preferably about 10 to 90 ° C, more preferably about 40 to 90 ° C.
- the content of the chain aggregated particles (f) of the ultrafine filler is preferably 6 to 40 parts by weight, more preferably 7 to 37 parts by weight with respect to 100 parts by weight of the polyfunctional acrylate monomer (d1). 8 to 35 parts by weight is more preferable.
- the polymerization initiator (e), the pigment (h), and titanium dioxide (g) are mixed with a composition in which the volatile monofunctional (meth) acrylate monomer (d2) is dissolved and dispersed.
- a dental color tone adjusting material (B) having a desired viscosity can be obtained.
- the chain aggregated particles (f ) In the polymerizable monomer composition in which the polyfunctional acrylate monomer (d1) and the volatile monofunctional (meth) acrylate monomer (d2) are mixed in advance, the chain aggregated particles (f ),
- the viscosity of the polymerizable monomer composition is not so high because the viscosity of the volatile monofunctional (meth) acrylate monomer (d2) is low, and a high shear force is applied during the kneading. I can't. Therefore, it becomes impossible to disperse the chain-like agglomerated particles of the ultrafine particle filler while crushing, and the viscosity of the resulting composition may be 5000 mPa ⁇ s or more.
- the dental color tone adjusting material (B) has a suppressed sedimentation of the pigment even at a low viscosity in the range of 20 to 100 mPa ⁇ s at 23 ° C., so that the dental color tone adjusting material (B) contains It is presumed that the chain-like agglomerated particles (f) of the ultrafine particle filler are not crushed to the state of primary particles completely. Produced in the same manner as the dental color adjusting material (B), except that the chain aggregated particles (f) of the ultrafine filler are replaced with ultrafine fillers that can be monodispersed in the form of primary particles without agglomeration. In the composition, the pigment tends to settle out even though the viscosity at 23 ° C. is in the range of 20 to 100 mPa ⁇ s.
- the compounding amount of titanium dioxide (g) is 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (d) and the chain aggregated particles (f) of the ultrafine particle filler. In the range of 0.1 to 1.5 parts by weight, preferably 0.3 to 1 part by weight.
- the average particle diameter of titanium dioxide (g) is not limited, but is preferably 0.1 to 10 ⁇ m from the viewpoint of the lubricity of the dental color adjusting material (B). When the average particle size is less than 0.1 ⁇ m, sufficient color developability may not be obtained. When the average particle diameter exceeds 10 ⁇ m, titanium dioxide may be easily precipitated.
- the average particle diameter of titanium dioxide (g) is more preferably 0.2 ⁇ m or more, further preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
- the method for measuring the average particle size of titanium dioxide (g) is the same as the method for measuring the average particle size of the ultrafine filler.
- Pigment (h) The pigment (h) used in the dental color tone adjusting material (B) means a pigment excluding titanium dioxide (g). Any known pigment (h) can be used without any limitation. Pigments are roughly classified into inorganic pigments and organic pigments, but they may be used in combination. Inorganic pigments include oxides, hydroxides, sulfides, chromates, silicates, sulfates, carbonates, ferrocyan compounds, phosphates, carbons, etc. Among them, oxides are preferably used. . Specific examples of the oxide include red iron oxide, yellow iron oxide, and black iron oxide.
- Red iron oxide is bengara and hematite, which is iron oxide represented by the chemical formula Fe 2 O 3 , and yellow iron oxide is goethite, iron oxide represented by the chemical formula FeOOH, and black iron oxide Is magnetite, which is iron oxide represented by the chemical formula Fe 3 O 4 .
- organic pigments examples include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, nitro pigments, nitroso pigments, and fluorescent pigments. Among them, azo pigments and phthalocyanine pigments are preferably used. Specific examples of the azo pigment include Novo Palm Yellow 4G, Chromophthal Yellow 3G, Chromophthal Yellow 3RLP, Novo Palm Red BN, Chromophthal Scarlet RN, Chromophthal Blue 4GNP, Blue No. 2 Aluminum Lake, and the like. . Specific examples of the phthalocyanine pigment include phthalocyanine blue and phthalocyanine green.
- the content of the pigment (h) is not limited, but from the viewpoint of the surface drying property of the dental color tone adjusting material (B), etc., chain aggregated particles (f) of the polymerizable monomer (d) and the ultrafine filler are used. For example, 0.001 to 30 parts by weight with respect to 100 parts by weight in total. When the pigment content is less than 0.001 part by weight, sufficient color tone may not be imparted. When content of a pigment exceeds 30 weight part, the dryness defect of a dental color tone adjustment material (B) may arise.
- the content of the pigment (h) is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the total amount of the polymerizable monomer (d) and the chain aggregated particles (f) of the ultrafine particle filler, It is 20 parts by weight or less, particularly 10 parts by weight or less, and more preferably 5 parts by weight or less.
- the average particle diameter of the pigment (h) is not limited, but is preferably from 0.1 to 10 ⁇ m from the viewpoint of the lubricity of the dental color adjusting material (B). When the average particle diameter of the pigment is less than 0.1 ⁇ m, sufficient color developability may not be obtained. When the average particle diameter of the pigment exceeds 10 ⁇ m, the pigment tends to settle.
- the average particle size of the pigment (h) is more preferably 0.2 ⁇ m or more, further preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
- the method for measuring the average particle size of the pigment (h) is the same as the method for measuring the average particle size of the ultrafine filler.
- both titanium dioxide (g) and pigment (h) in the dental color tone adjusting material (B) it becomes easy to adjust the color tone of the dental color tone adjusting material (B) after curing. It becomes possible to adjust the color tone close to natural teeth. Moreover, it becomes difficult to produce a change in the color tone of the dental color tone adjusting material before curing and the color tone of the dental color tone adjusting material after curing. Further, even if the coating thickness is thin, it is possible to adjust the color tone to a desired color tone, for example, a color tone that approximates natural teeth, and the color change due to the coating thickness is reduced. This effect is surely obtained when both the titanium dioxide (g) and the pigment (h) are contained at the above-mentioned preferable contents.
- an ultraviolet absorber an antioxidant, a polymerization inhibitor, an X-ray contrast agent, a thickener, a fluorescent agent and the like are further added within a range that does not impair the effects of the invention. Is also possible.
- fluoride ion sustained release such as fluoroaluminosilicate glass, calcium fluoride, sodium fluoride, sodium monofluorophosphate, etc.
- a filler can also be added.
- the dental color tone adjustment material kit of the present invention is an inlay made from an organic / inorganic dental restoration material, porcelain, ceramics, or a zirconia sintered body block, glass block, or resin block processed by CAD / CAM. Suitable for color adjustment of dental restoration materials such as onlays and crowns. From another aspect, the present invention provides a color tone adjusting material kit for a dental restoration material comprising the dental color tone adjusting material kit according to the present invention.
- the present invention includes embodiments in which the above configurations are combined in various ways within the technical scope of the present invention as long as the effects of the present invention are exhibited.
- UDMA [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate
- U-4TH N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) Propane-1,3-diol] tetramethacrylate
- 3G triethylene glycol dimethacrylate
- TMDPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
- CQ dl-camphorquinoneamine: ethyl 4- (N, N-dimethylamino) benzoate
- Ar380 AEROSIL registered trademark
- Silane treatment OX50 AEROSIL (registered trademark) OX50 (average primary particle size 40 nm) manufactured by Nippon Aerosil Co., Ltd. was dispersed in 500 mL of water, 8 g of 3-methacryloyloxypropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure and further dried at 90 ° C. for 3 hours to obtain silane-treated OX50.
- Silane treatment AL-C Aeroxide (registered trademark) Alu C (average primary particle size 20 nm) manufactured by Nippon Aerosil Co., Ltd. was dispersed in 500 mL of water, 15 g of 3-methacryloyloxypropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and further dried at 90 ° C. for 3 hours to obtain silane-treated AL-C.
- AL-C Aeroxide (registered trademark) Alu C (average primary particle size 20 nm) manufactured by Nippon Aerosil Co., Ltd. was dispersed in 500 mL of water, 15 g of 3-methacryloyloxypropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and further dried at 90 ° C. for 3 hours to obtain silane-treated AL-C.
- Silane-treated NF180 200 g of barium boroaluminosilicate glass powder (GM278884, NF180, average primary particle size 0.18 ⁇ m, manufactured by Schott) was dispersed in 500 mL of water, 8 g of 3-methacryloyloxypropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and surface treatment was performed by further drying at 90 ° C. for 3 hours to obtain silane-treated NF180.
- barium boroaluminosilicate glass powder GM278884, NF180, average primary particle size 0.18 ⁇ m, manufactured by Schott
- Silane-treated monodisperse ultrafine particle filler Silica / alumina water monodisperse sol (manufactured by JGC Catalysts & Chemicals, Cataloid-SN, average primary particle size 12 nm, silica / alumina concentration 20% by weight) is used, and water is replaced with methanol. As a result, a methanol monodispersed sol having a solid concentration of 20% by weight was obtained. After mixing the sol and ethanol, 3-methacryloyloxypropyltrimethoxysilane was added to the mixture to obtain a monodispersed sol in which the surface of the silica / alumina particles was modified with 3-methacryloyloxypropyltrimethoxysilane. .
- the solvent of the obtained monodispersed sol was substituted with methyl methacrylate to obtain a silica / alumina methyl methacrylate monodispersed sol whose surface was modified with 3-methacryloyloxypropyltrimethoxysilane.
- Titanium dioxide Pigment White 6 Average particle size 0.2 ⁇ m
- Example 1 3 g of MDP (3 parts by weight) and 97 g of ethanol (97 parts by weight) were mixed to obtain 100 g of a uniform liquid composition. This composition was designated as primer composition 1.
- Primer compositions 2 to 23 were prepared in the same manner as in Example 1 with the weight ratios shown in Table 1 or Table 2. Using this primer composition and the dental color tone adjusting material composition 1 prepared in Example 1, tests were conducted according to the surface drying test, tensile adhesion test, coffee coloring test, and abrasion resistance test method described later. . The results are shown in Tables 1 and 2.
- Examples 18 to 32, Comparative Examples 7 to 14 A dental color adjusting material composition was prepared in the same manner as in Example 1 with the weight ratios shown in Table 3. Using the primer composition 1 obtained in Example 1 and this dental color-adjusting material composition, testing was conducted according to the following surface drying test, coffee coloring test, abrasion resistance test, lubrication durability test, and viscosity measurement. Carried out. The results are shown in Tables 3 and 4.
- Example 36 The primer composition 1 was applied to a “VITA classic” A2 shade guide subjected to sandblasting, and the surface was air blown to dry the applied primer until the fluidity of the primer disappeared. Next, the dental color tone adjusting material composition 1 was applied once with a flat brush (application thickness: about 20 ⁇ m), and irradiated with light for 90 seconds using a technical irradiator ⁇ Light III (Morita). The obtained sample was visually compared with a “VITA classic” A3 shade guide to confirm that the color tone was equivalent.
- Example 37 The same operation as in Example 36 was performed except that the dental color tone adjusting material composition 1 was applied twice with a flat brush (application thickness: about 40 ⁇ m). The obtained sample was visually compared with a “VITA classic” A3.5 shade guide, and it was confirmed that the color tone was equivalent.
- Example 38 Except for yellow pigment (0.11 parts by weight) 0.011 g, red pigment (0.02 parts by weight) 0.002 g, and black pigment (0.1 parts by weight) 0.01 g, the same operation as in Example 1 was performed.
- a dental color tone adjusting material composition 24 was prepared. The operation was performed in the same manner as in Example 36 except that the dental color tone adjusting material composition 24 to be used was used. The obtained sample was visually compared with a “VITA classic” B2 shade guide and confirmed to have an equivalent color tone.
- Example 39 The operation was performed in the same manner as in Example 38 except that the dental color tone adjusting material composition 24 was applied twice with a flat brush (application thickness: about 40 ⁇ m). The obtained sample was visually compared with a “VITA classic” B3 shade guide to confirm that the color tone was equivalent.
- Example 40 Titanium dioxide (0.5 part by weight) 0.05 g, yellow pigment (0.06 part by weight) 0.006 g, red pigment (0.01 part by weight) 0.001 g, black pigment (0.24 part by weight) Except for 24 g, the same operation as in Example 1 was performed to prepare a dental color tone adjusting material composition 25. The same operation as in Example 36 was performed except that the dental color tone adjusting material composition 25 to be used was used. The obtained sample was visually compared with a “VITA classic” C2 shade guide and confirmed to have an equivalent color tone.
- Example 41 The same operation as in Example 40 was performed, except that the dental color tone adjusting material composition 25 was applied twice with a flat brush (application thickness: about 40 ⁇ m). The obtained sample was visually compared with a “Vita classic” C3 shade guide, and it was confirmed that the color tone was equivalent.
- Example 19 The operation was performed in the same manner as in Example 36 except that the dental color tone adjusting material composition 20 was applied once with a flat brush (application thickness: about 20 ⁇ m). The obtained sample was visually compared with a “VITA classic” A2 shade guide, and it was confirmed that the sample had a whitish color and did not have a desired color tone.
- Example 20 The operation was performed in the same manner as in Example 36 except that the dental color tone adjusting material composition 21 was applied once with a flat brush (application thickness: about 20 ⁇ m). The obtained sample was visually compared with a “VITA classic” A2 shade guide, and it was confirmed that the color tone did not change and the desired color tone was not obtained.
- An area-defining tape was prepared by punching a 5 mm hole in a 0.13 mm thick tape. This tape was affixed to the resin surface and the adhesion area was specified to be 5 mm.
- the primer composition of each Example and Comparative Example was applied to a specified area, and the surface was air blown to dry the applied primer until the fluidity of the primer disappeared.
- the dental color tone adjusting material composition of each Example and Comparative Example was applied, and polymerized by light irradiation for 90 seconds with a technical irradiator ⁇ Light III (manufactured by Morita). The polymerized surface was lightly sandblasted and washed, and then a stainless steel rod sandblasted with Panavia 21 was planted. Five test pieces were prepared.
- the crosshead speed was set to 2 mm / min with a universal measuring tester (manufactured by Shimadzu Corporation, Autograph AG-100kNI).
- the obtained test force was divided by the adhesion area to give the adhesion strength, and the numeric value of the adhesion strength was the average value of the measured values for the five test pieces.
- the bond strength is preferably 5 MPa or more, more preferably 7 MPa or more, and most preferably 10 MPa or more.
- a plate was made.
- the surface of the cured plate was polished with # 3000 water-resistant abrasive paper, and further buffed with 3 ⁇ m diamond paste to obtain a mirror-polished surface.
- the primer composition of each Example and Comparative Example was applied to the surface of the cured plate, and the surface was air blown to dry the applied primer until the fluidity of the primer disappeared.
- a spacer having a thickness of 100 ⁇ m, an outer diameter of 15 mm, and an inner diameter of 10 mm was attached.
- Fill the hole with the dental color tone adjusting material composition of each example and comparative example remove the surplus with a razor blade, smooth the surface, and irradiate light for 90 seconds with the Technical Irradiator ⁇ Light III (Morita) And polymerized.
- SE6000 color difference meter
- the color tone of the test piece before the test was measured using the light source as a D65 / 2 light source.
- the test piece was immersed in 99.5 wt% ethanol at room temperature for 24 hours, then re-immersed in a 2 wt% coffee aqueous solution, and stored at 37 ° C. for 3 days.
- the test piece was taken out, washed lightly with running water, and dried with weak air.
- the color tone of the test piece after the test was measured with a color difference meter.
- the difference in color tone ( ⁇ E *) before and after the test was obtained and used as an index for the coffee discoloration.
- the chromaticity before the test was L * 1 , a * 1 , and b * 1 .
- the chromaticity after the test was L * 2 , a * 2 , and b * 2 .
- Abrasion resistance test A mold with a width of 20 x length of 30 x thickness of 2 mm is filled with hard resin for dental crown: Estenia C & B (E4 manufactured by Kurarenorita Dental Co., Ltd.), and irradiated with both sides of the front and back with a technical irradiation device " ⁇ Light III" for 180 seconds. And a cured product was obtained. The surface of the cured product was polished with # 3000 water-resistant abrasive paper, and further buffed with 3 ⁇ m diamond paste to obtain a mirror-polished surface. A rough surface was prepared using carborundum in a 10 mm square range at the center of the polished surface.
- each Example and Comparative Example was applied to the rough surface, and the surface was air blown to dry the applied primer until the fluidity of the primer disappeared. Subsequently, the dental color tone adjusting material composition of each Example and Comparative Example was applied and polymerized by light irradiation for 180 seconds with a technical irradiator ⁇ Light III (manufactured by Morita). A color difference meter (“SE6000” manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the color tone of the central part (composition coated surface) of the test piece before the test using a D65 / 2 light source as the light source.
- a slurry of 40% by weight of toothpaste (manufactured by Lion Corporation, trade name “White & White”) and 60% by weight of distilled water is prepared, and a toothbrush (manufactured by Lion Corporation, trade name “Bitoine”) is formed on the surface layer in the slurry.
- the toothbrush was slid back and forth 40,000 times with a swinging width of 10 cm with a load of 250 g applied.
- the color tone of the test piece center part (composition application surface) after the test was measured.
- the chromaticity before the test was L * 1 , a * 1 , and b * 1 .
- the chromaticity after the test was L * 2 , a * 2 , and b * 2 .
- a mold with a width of 20 x length of 30 x thickness of 2 mm is filled with hard resin for dental crown: Estenia C & B (E4 made by Kurarenorita Dental Co., Ltd.), and the front and back sides are 180 seconds with a technical irradiator "Light III (Morita)"
- the surface of the cured product was polished with # 3000 water-resistant abrasive paper and then buffed with 3 ⁇ m diamond paste to obtain a mirror-polished surface with a 10 mm square area in the center of the polished surface.
- a rough surface was prepared using carborundum, and the primer composition of each example and comparative example was applied to the rough surface, and the surface was air blown to dry until the fluidity of the applied primer disappeared.
- the dental color tone adjusting material composition of each example and comparative example was applied and polymerized by irradiation with light for 180 seconds with a technical irradiator ⁇ light III (manufactured by Morita).
- the toothbrush (product name" Bitoine ", hardness normal) bristles on the surface of the surface layer in the slurry, The toothbrush was swung back and forth 40,000 times with a swinging width of 10 cm with a load of 250 g applied. Thereafter, the glossiness of this surface was shown as a ratio (glossiness) with a gloss meter (Nippon Denshoku Co., Ltd. “VG2000”) when the mirror was 100%. The measurement angle was 60 degrees.
- the glossiness (sliding durability) is preferably 40% or more, more preferably 45% or more, and still more preferably 55% or more.
- the dental color tone adjusting material composition of each example and comparative example was applied in a thickness of 50 ⁇ m, and polymerized by irradiation with light for 180 seconds with a technical irradiator ⁇ light III (manufactured by Morita).
- the obtained cured product was designated as a chromaticity plate 2.
- the light source is a D65 / 2 light source, and a standard white plate is placed behind the test piece to determine the chromaticity (Lab). It was measured.
- a chromaticity plate was prepared in the same manner as described above except that the thickness of the dental color tone adjusting material composition of each example and comparative example was 80 ⁇ m and 130 ⁇ m, and the chromaticity was measured.
- the chromaticity of the chromaticity plate 1 is set to L 1 , a 1 , and b 1 .
- Chromaticity chromaticity plate 2 was L 2, a 2, b 2 .
- the color difference ( ⁇ E) was calculated by the following formula.
- ⁇ E ((L 1 ⁇ L 2 ) 2 + (a 1 ⁇ a 2 ) 2 + (b 1 ⁇ b 2 ) 2 ) 0.5
- the slope of the linear regression line is calculated with the application thickness of the color tone adjusting material as the X value and ⁇ E as the Y value. It is preferable that the inclination is 0.1 or less and becomes a value larger than 0.
- Comparative Example 18 the value of ⁇ E measured in the color tone imparting test itself was 10 or less in all thicknesses of 50 ⁇ m, 80 ⁇ m, and 130 ⁇ m. The value of ⁇ E was too small, and Comparative Example 18 could not provide a sufficient color tone.
- the dental color tone adjusting material kit of the present invention has good surface dryness, excellent adhesion to an adherend (especially a dental restoration material), and the dental color tone adjusting material after curing is changed by coffee or the like. Coloring hardly occurs, wear resistance is improved, sufficient color tone can be imparted, and adjustment to a desired color tone is possible even when the coating thickness is thin. Moreover, since the dental color tone adjusting material kit of the present invention can also suppress sedimentation of the pigment, color unevenness or the like does not occur.
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Abstract
Description
プライマー組成物(A)と歯科用色調調整材(B)とを含む歯科用色調調整材キットであって、
前記プライマー組成物(A)は、酸性基含有重合性単量体(a)と揮発性有機溶剤(b)とを含有し、
前記歯科用色調調整材(B)は、重合性単量体(d)、重合開始剤(e)、集塊粒子(f)、二酸化チタン(g)及び顔料(h)を含有し、
前記酸性基含有重合性単量体(a)の含有量は、前記プライマー組成物(A)の全重量の0.05~45重量%の範囲にあり、
前記揮発性有機溶剤(b)の含有量は、前記プライマー組成物(A)の全重量の55~99.95重量%の範囲にあり、
前記重合性単量体(d)は、1分子中に3個以上のアクリロイル基を持つ多官能アクリレート単量体(d1)と揮発性単官能(メタ)アクリレート単量体(d2)とを含有し、
前記単量体(d1)と前記単量体(d2)の合計量は、前記重合性単量体(d)の重量に対し88重量%以上であり、
前記集塊粒子(f)は、平均一次粒子径が1~50nmである超微粒子フィラーの鎖状の集塊粒子であり、
前記集塊粒子(f)の含有量は、前記重合性単量体(d)と前記集塊粒子(f)との合計重量100重量部に対し5~20重量部の範囲にあり、
前記二酸化チタン(g)の含有量は、前記重合性単量体(d)と前記集塊粒子(f)との合計重量100重量部に対し0.05~2重量部の範囲にあり、
前記顔料(h)は、前記二酸化チタン(g)を除く顔料である、
歯科用色調調整材キット、により上記の目的を達成した。
まず、プライマー組成物(A)について詳細に説明する。プライマー組成物(A)は、歯科用色調調整材(B)を使用する前に使用することが意図されている。プライマー組成物(A)を使用することによって、歯科用色調調整材(B)と歯又は歯冠修復材のような歯科用修復材等の被着体、特に歯科用修復材との接着性が向上する。その結果、歯科用色調調整材(B)の塗布後数日経過しても、硬化後の歯科用色調調整材(B)と被着体の間にコーヒー等が侵入することによる変着色が生じにくい。
プライマー組成物(A)に含まれる酸性基含有重合性単量体(a)は、重合可能な構造を有し、重合により硬化体を形成する。また、酸性基含有重合性単量体(a)を用いることにより、プライマー組成物(A)の被着体表面に対する接着性が向上する。酸性基含有重合性単量体(a)としては、リン酸基、ピロリン酸基、チオリン酸基、ホスホン酸基、スルホン酸基、カルボン酸基等の酸性基を少なくとも1個有し、更にアクリロイル基、メタクリロイル基、ビニル基、スチレン基等の重合性基を少なくとも1個有する重合性単量体が挙げられる。下記に酸性基含有重合性単量体(a)の具体例を挙げる。
本発明において、揮発性有機溶剤(b)は、常圧における沸点が120℃以下であり、25℃で液体状態である有機溶媒を意味する。具体的には、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、2-メチル-プロパノール、アセトン、メチルエチルケトン、テトラヒドロフラン、ジエチルエーテル、ジイソプロピルエーテル、ヘキサン、トルエン、クロロホルム、酢酸エチル、メチルアクリレート、メチルメタクリレート、エチルメタクリレート等が挙げられる。中でも安全性及び揮発性を考慮すると、エタノール、2-プロパノール、2-メチル-2-プロパノール、アセトン、メチルメタクリレートが好適である。なお、酸性基含有重合性単量体(a)及び揮発性有機溶剤(b)の両方に該当する化合物は、酸性基含有重合性単量体(a)に該当するものとする。
プライマー組成物(A)は、更にシランカップリング剤(c)を含有することができる。シランカップリング剤(c)は、被着体のシラノール基と脱水縮合をすることにより、プライマー組成物(A)と被着体との接着効果を向上させる。シランカップリング剤(c)としては、公知のシランカップリング剤が何ら制限することなく使用できる。例えば、3-(メタ)アクリロイルオキシプロピルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルトリエトキシシラン、3-(メタ)アクリロイルオキシプロピルトリヘキシロキシシラン、6-(メタ)アクリロイルオキシヘキシルトリメトキシシラン、6-(メタ)アクリロイルオキシヘキシルトリエトキシシラン、8-(メタ)アクリロイルオキシオクチルトリメトキシシラン、10-(メタ)アクリロイルオキシデシルトリメトキシシラン、11-(メタ)アクリロイルオキシウンデシルトリメトキシシラン、11-(メタ)アクリロイルオキシウンデシルトリエトキシシラン、11-(メタ)アクリロイルオキシウンデシルトリヘキシロキシシラン、20-(メタ)アクリロイルオキシエイコシルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3-(メタ)アクリロイルオキシプロピルジメチエトキシシラン、11-(メタ)アクリロイルオキシウンデシルメチルジエトキシシラン、3-(メタ)アクリロイルオキシプロピルフェニルジメトキシシラン、3-(メタ)アクリロイルオキシプロピルトリクロロシラン、11-(メタ)アクリロイルオキシウンデシルトリクロロシラン、3-(メタ)アクリロイルオキシプロピルジクロロメチルシラン、3-(メタ)アクリロイルオキシプロピルクロロジメチルシラン、11-(メタ)アクリロイルオキシウンデシルジクロロメチルシラン、11-(メタ)アクリロイルオキシウンデシルクロロジエチルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリアセトキシシラン、ビニルジクロロメチルシラン、ビニルトリ(2-メトキシエトキシ)シラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、アリルトリエトキシシラン、ジアリルジクロロシラン、ジビニルジエトキシシラン、m,p-スチリルエチルトリメトキシシラン、3,4-エポキシシクロヘキシルメチルトリメトキシシランが挙げられる。プライマー組成物(A)と被着体との接着性及び取り扱い性の観点から、3-(メタ)アクリロイルオキシプロピルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3-アミノプロピルトリエトキシシラン、11-メタクリロイルオキシウンデシルトリメトキシシラン及びこれらの加水分解物が好ましい。
続いて、歯科用色調調整材(B)について詳細に説明する。歯科用色調調整材(B)は、プライマー組成物(A)の使用の後に使用されることが意図されている。プライマー組成物(A)と組み合わせて用いることによって、歯科用色調調整材(B)の表面乾燥性が向上し、硬化後の歯科用色調調整材の変色が生じにくく、耐着色性、耐摩耗性が向上する。
歯科用色調調整材(B)に含まれる重合性単量体(d)は、1分子中に3個以上のアクリロイル基を持つ多官能アクリレート単量体(d1)及び揮発性単官能(メタ)アクリレート単量体(d2)を含む。多官能アクリレート単量体(d1)と揮発性単官能(メタ)アクリレート単量体(d2)との合計量は、重合性単量体(d)の全重量に対し、88重量%以上である。歯科用色調調整材(B)の表面乾燥性の観点より、多官能アクリレート単量体(d1)と揮発性単官能(メタ)アクリレート単量体(d2)との合計量は、重合性単量体(d)の全重量に対し、94重量%以上が好ましく、98重量%以上がより好ましい。重合性単量体(d)が多官能アクリレート単量体(d1)及び揮発性単官能(メタ)アクリレート単量体(d2)のみからなることが更に好ましい。
多官能アクリレート単量体(d1)は、1分子中に3個以上のアクリロイル基を有する。多官能アクリレート単量体(d1)としては、例えば、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、テトラメチロールメタントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、2,2,6,6-テトラキス(アクリロイルオキシメチル)-4-オキサヘプタン-1,7-ジオール1-アクリラート等が挙げられる。特に、取り扱い性及び安全性の観点から、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールヘキサアクリレートが好ましい。
本発明において、揮発性単官能(メタ)アクリレート単量体(d2)は、常圧における沸点が120℃以下であり、25℃で液体である単官能(メタ)アクリレート単量体を意味する。揮発性単官能(メタ)アクリレート単量体(d2)としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート等が挙げられる。毒性が低く、沸点が低いという観点から、メチルメタクリレートが最も好ましい。
イソブチル(メタ)アクリレート、ベンジル(メタ)アクリレート、ラウリル(メタ)アクリレート、2-(N,N-ジメチルアミノ)エチル(メタ)アクリレート、2,3-ジブロモプロピル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、プロピレングリコールモノ(メタ)アクリレート、グリセリンモノ(メタ)アクリレート、エリトリトールモノ(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、N-ヒドロキシエチル(メタ)アクリルアミド、N-(ジヒドロキシエチル)(メタ)アクリルアミド、(メタ)アクリロイルオキシドデシルピリジニウムブロマイド、(メタ)アクリロイルオキシドデシルピリジニウムクロライド、(メタ)アクリロイルオキシヘキサデシルピリジニウムクロライド、(メタ)アクリロイルオキシデシルアンモニウムクロライド等が挙げられる。
エチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、ビスフェノールAジグリシジル(メタ)アクリレート(2,2-ビス[4-〔3-(メタ)アクリロイルオキシ-2-ヒドロキシプロポキシ〕フェニル]プロパン、通称Bis-GMA)、2,2-ビス〔4-(メタ)アクリロイルオキシエトキシフェニル〕プロパン、1,2-ビス〔3-(メタ)アクリロイルオキシ-2-ヒドロキシプロポキシ〕エタン、ペンタエリトリトールジ(メタ)アクリレート、[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、N,N-(2,2,4-トリメチルヘキサメチレン)ビス〔2-(アミノカルボキシ)プロパン-1,3-ジオール〕テトラメタクリレート等が挙げられる。
歯科用色調調整材(B)に含有される重合開始剤(e)としては、一般的に使用可能な重合開始剤から選択して使用でき、特に歯科用途に用いられている重合開始剤が好ましく用いられる。なかでも、光重合又は化学重合の重合開始剤を、単独で又は2種以上適宜組み合わせて使用できる。
歯科用色調調整材(B)が含有する超微粒子フィラーの鎖状の集塊粒子(f)は、歯科用色調調整材(B)の表面硬度を向上し、滑沢耐久性が優れたものとする機能を有する。また、歯科用色調調整材(B)にチクソトロピー性を与え、塗布しやすい粘度に調整する機能、及び同時に配合する顔料(h)の沈降抑制作用も有する。超微粒子フィラーの鎖状の集塊粒子(f)は、硬化後の歯科用色調調整材(B)の表面滑沢性の観点から平均一次粒子径が1~50nmのものが用いられ、5~50nmがより好ましい。本発明において、前記超微粒子フィラーの平均粒子径は、超微粒子の走査型電子顕微鏡(日立製作所製、S-4000型)写真を撮影し、その写真の単位視野内に観察される粒子(200個以上)の粒子径を、画像解析式粒度分布ソフトウェア(Macview(株式会社マウンテック))を用いて測定することにより、求めることができる。このとき、粒子の粒子径は、その粒子と同一の面積を持つ円の直径である円相当径として求められ、粒子の数とその粒子径より、平均一次粒子径が算出される。種類、形状は、特に限定されるものではなく公知の超微粒子フィラーの鎖状の集塊粒子を用いることができる。親水性の超微粒子フィラーの鎖状の集塊粒子と疎水性の超微粒子フィラーの鎖状の集塊粒子を併用して使用しても構わない。これに対し、一次粒子が集塊することなく単分散状態で存在する超微粒子フィラーは、歯科用色調調整材(B)に配合しても粘度の調整ができず、また顔料の沈降も抑制できないため、色むら等を生じやすく好ましくない。
歯科用色調調整材(B)に含有される二酸化チタン(g)は、光の散乱により白色の外観色を与える。二酸化チタン(g)は隠蔽力が高い。このため、二酸化チタン(g)を含有する歯科用色調調整材(B)を薄く塗布しても、被着体の色補正が可能となり、また、厚みによる着色変化が少なくなる。また、適度な含有量とすることにより、歯科用修復材料の有する天然歯に近似した透明感が損なわれない。配合量が少なすぎると、隠蔽力が不足し、歯科用修復材料の色調調整が困難となることがあり、また塗布厚みに従って、濃い色調となるため、塗りムラが生じやすい。また、配合量が多すぎると、歯科用色調調整材(B)が不透明となりすぎ、審美性が低下することがあり、また歯科用色調調整材(B)の表面乾燥性が低下するため、着色されやすくなったり滑沢耐久性が低下したりすることがある。二酸化チタン(g)の配合量は、重合性単量体(d)と超微粒子フィラーの鎖状の集塊粒子(f)との合計量100重量部に対して、0.05~2重量部の範囲にあり、0.1~1.5重量部が好ましく、0.3~1重量部が更に好ましい。
歯科用色調調整材(B)に用いられる顔料(h)は、二酸化チタン(g)を除く顔料を意味する。顔料(h)は、公知のものが、なんら制限なく使用できる。顔料は、無機顔料と有機顔料に大別されるが、混合して使用しても構わない。無機顔料としては、酸化物、水酸化物、硫化物、クロム酸塩、珪酸塩、硫酸塩、炭酸塩、フェロシアン化合物、リン酸塩、炭素等が挙げられ、中でも酸化物が好適に用いられる。酸化物としては、具体的には、赤酸化鉄、黄酸化鉄、黒酸化鉄等が挙げられる。赤酸化鉄とは、ベンガラ、ヘマタイトであり、化学式Fe2O3で示される酸化鉄であり、黄酸化鉄とは、ゲーサイトであり、化学式FeOOHで示される酸化鉄であり、黒酸化鉄とは、マグネタイトであり、化学式Fe3O4で示される酸化鉄である。
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
M12P:12-メタクリロイルオキシドデシルジハイドロジェンホスフェート
EtOH:エタノール
MMA:メチルメタクリレート
KBM503:3-メタクリロイルオキシプロピルトリメトキシシラン
KBE903:3-アミノプロピルトリエトキシシラン
11-MUS:11-メタクリロイルオキシウンデシルトリメトキシシラン
DPE-6A:ジペンタエリスリトールヘキサアクリレート
PE-3A:ペンタエリスリトールトリアクリレート
MMA:メチルメタクリレート
EMA:エチルメタクリレート
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
U-4TH:N,N-(2,2,4-トリメチルヘキサメチレン)ビス〔2-(アミノカルボキシ)プロパン-1,3-ジオール〕テトラメタクリレート
3G:トリエチレングリコールジメタクリレート
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
CQ:dl-カンファーキノン
アミン:4-(N,N-ジメチルアミノ)安息香酸エチル
R972:日本アエロジル製「R972」 平均一次粒子径:16nm
日本アエロジル社製、AEROSIL(登録商標)Ar380(平均一次粒子径7nm)を、水500mLに分散し、3-メタクリロイルオキシプロピルトリメトキシシラン8gを加えて室温で2時間攪拌した。溶媒を減圧留去し、更に90℃で3時間乾燥することにより、シラン処理Ar380を得た。
日本アエロジル社製、AEROSIL(登録商標)OX50(平均一次粒子径40nm)を、水500mLに分散し、3-メタクリロイルオキシプロピルトリメトキシシラン8gを加えて室温で2時間攪拌した。溶媒を減圧留去し、更に90℃で3時間乾燥することにより、シラン処理OX50を得た。
日本アエロジル社製、アエロキサイド(登録商標)Alu C(平均一次粒子径20nm)を、水500mLに分散し3-メタクリロイルオキシプロピルトリメトキシシラン15gを加えて室温で2時間攪拌した。溶媒を減圧留去し、更に90℃で3時間乾燥することにより、シラン処理AL-Cを得た。
シラン処理NF180
バリウムボロアルミノシリケートガラス粉末(ショット社製GM27884、NF180、平均一次粒子径0.18μm)200gを水500mLに分散し、3-メタクリロイルオキシプロピルトリメトキシシラン8gを加えて室温で2時間攪拌した。溶媒を減圧留去し、更に90℃で3時間乾燥することによって表面処理して、シラン処理NF180を得た。
シリカ・アルミナ水単分散ゾル(日揮触媒化成社製、Cataloid-SN、平均一次粒子径12nm、シリカ・アルミナ濃度20重量%)を使用し、水をメタノールに溶媒置換して固形分濃度20重量%のメタノール単分散ゾルを得た。このゾルとエタノールを混合した後、この混合液に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添加し、シリカ・アルミナ粒子の表面が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修飾された単分散ゾルを得た。次に、得られた単分散ゾルの溶媒をメチルメタクリレートに置換し、表面が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修飾されたシリカ・アルミナのメチルメタクリレート単分散ゾルを得た。
二酸化チタン:PigmentWhite6 平均粒子径0.2μm
黄顔料:ノボパームイエロー4G 平均粒子径0.2μm
赤顔料:ノボパームレッドBN 平均粒子径0.2μm
黒顔料:鉄黒 平均粒子径0.2μm
MDP(3重量部)3gとエタノール(97重量部)97gとを混和して均一な液状組成物100gを得た。この組成物をプライマー組成物1とした。
表1又は表2に記載の重量比でプライマー組成物2~23を実施例1と同様に作製した。このプライマー組成物と実施例1で作製した歯科用色調調整材組成物1とを使用して、後述する、表面乾燥性試験、引張り接着試験、コーヒー着色試験、耐摩耗試験方法に従って試験を実施した。結果を表1及び表2に示す。
表3に記載の重量比で歯科用色調調整材組成物を実施例1と同様に作製した。実施例1で得たプライマー組成物1とこの歯科用色調調整材組成物とを使用して、後述の表面乾燥性試験、コーヒー着色試験、耐摩耗試験、滑沢耐久性試験、粘度測定に従って試験を実施した。結果を表3及び表4に示す。
50mlの蓋のついたガラス製容器(スクリュー管瓶、アズワン社製)に上記で作製したシリカ・アルミナのメチルメタクリレート単分散ゾル(MMA:40重量部、単分散超微粒子フィラー:10重量部)5gを入れ、その中にTMDPO(3重量部)0.3g、黄顔料(0.09重量部)0.009g、赤顔料(0.01重量部)0.001g、黒顔料(0.1重量部)0.01g、及び二酸化チタン(0.6重量部)0.06gを入れて、氷浴中で1時間超音波洗浄機にかけ、液状組成物を得た。液状組成物の中に、DPE-6A(50重量部)5gを投入し、ミックスローター(アズワン社製)を用いて、一晩混合し、歯科用色調調整材組成物22を得た。
プライマー組成物1と、歯科用色調調整材組成物1、6、7、21、23、20とを使用して、色調付与性試験方法に従って、測定した。結果を表5に示す。
サンドブラスト処理を施した「VITA classical」のA2シェードガイドに、プライマー組成物1を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、歯科用色調調整材組成物1を平筆で1回塗布し(塗布厚み:約20μm)、技工用照射器αライトIII(モリタ社製)で90秒間光照射した。得られた試料を「VITA classical」のA3シェードガイドと目視で比較し、同等の色調であることを確認した。
歯科用色調調整材組成物1を平筆で2回塗布(塗布厚み:約40μm)した以外は、実施例36と同様に操作を行った。得られた試料を「VITA classical」のA3.5シェードガイドと目視で比較し、同等の色調であることを確認した。
黄顔料(0.11重量部)0.011g、赤顔料(0.02重量部)0.002g、黒顔料(0.1重量部)0.01g以外は、実施例1と同様に操作を行い、歯科用色調調整材組成物24を作製した。使用する歯科用色調調整材組成物24を使用する以外は、実施例36と同様に操作を行った。得られた試料を「VITA classical」のB2シェードガイドと目視で比較し、同等の色調であることを確認した。
歯科用色調調整材組成物24を平筆で2回塗布(塗布厚み:約40μm)した以外は、実施例38と同様に操作を行った。得られた試料を「VITA classical」のB3シェードガイドと目視で比較し、同等の色調であることを確認した。
二酸化チタン(0.5重量部)0.05g、黄顔料(0.06重量部)0.006g、赤顔料(0.01重量部)0.001g、黒顔料(0.24重量部)0.24g以外は、実施例1と同様に操作を行い、歯科用色調調整材組成物25を作製した。使用する歯科用色調調整材組成物25を使用する以外は、実施例36と同様に操作を行った。得られた試料を「VITA classical」のC2シェードガイドと目視で比較し、同等の色調であることを確認した。
歯科用色調調整材組成物25を平筆で2回塗布(塗布厚み:約40μm)した以外は、実施例40と同様に操作を行った。得られた試料を「VITA classical」のC3シェードガイドと目視で比較し、同等の色調であることを確認した。
歯科用色調調整材組成物20を平筆で1回塗布(塗布厚み:約20μm)した以外は、実施例36と同様に操作を行った。得られた試料を「VITA classical」のA2シェードガイドと目視で比較し、白っぽい色となって、所望の色調となっていないことを確認した。
歯科用色調調整材組成物21を平筆で1回塗布(塗布厚み:約20μm)した以外は、実施例36と同様に操作を行った。得られた試料を「VITA classical」のA2シェードガイドと目視で比較し、色調が変化しておらず、所望の色調となっていないことを確認した。
サンドブラスト処理を施した「VITA classical」のシェードガイドに、各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、各実施例及び比較例の歯科用色調調整材組成物を塗布し、技工用照射器αライトIII(モリタ社製)で90秒間光照射した。色調調整材をウエス(十条キンバリー社、JKワイパー150-S)で強くこすり、未重合モノマーや傷の有無を目視にて判断した。傷のついていないものは、表面が乾燥していると判断して○とした。わずかに傷が認められるものは△とし、多数の傷のついたものは表面乾燥していないと判断して×とした。
被着体として、歯冠用硬質レジン:エステニアC&B(E4 クラレノリタケデンタル社製)を使用し、10×10×2mmの硬化板をメーカー指示の通りに重合し作製した。作製した硬化板をパナビア21(クラレノリタケデンタル社製)で12×12×2mmのステンレス板に裏打ちした。レジン表面を#3000耐水研磨紙で研磨した後、更に3μmのダイヤモンドペーストでバフ研磨し鏡面研磨面とした。超音波洗浄機で洗浄いて流水で水洗後、エアブローして乾燥させた。0.13mm厚みのテープにФ5mmの穴を空け、面積規定テープを作製した。このテープをレジン表面に貼り付け接着面積をФ5mmに規定した。規定面積に各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、各実施例及び比較例の歯科用色調調整材組成物を塗布し、技工用照射器αライトIII(モリタ社製)で90秒間光照射し重合させた。重合した面にサンドブラスト処理を軽く施し、洗浄した後、パナビア21でサンドブラスト処理したステンレス棒を植立させた。試験片を5個作製した。37℃水中に24時間浸漬保管した後、万能測定試験機(島津製作所社製、オートグラフAG-100kNI)でクロスヘッドスピードを2mm/分に設定して測定した。得られた試験力を接着面積で割り、接着強さとし、接着強さの数値は、5個の試験片についての測定値の平均値とした。接着強さは、5MPa以上が好ましく、7MPa以上が更に好ましく、10MPa以上が最も好ましい。
Ф15×1mmの金型に歯冠用硬質レジン:エステニアC&B(E4、クラレノリタケデンタル社製)を充填し、技工用照射器αライトIII(モリタ社製)で180秒間光照射し重合させ、硬化板を作製した。硬化板表面を#3000耐水研磨紙で研磨した後、更に3μmのダイヤモンドペーストでバフ研磨し鏡面研磨面を得た。硬化板表面に、各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、厚み100μm、外径15mm内径10mmのスペーサーを貼り付けた。穴部に各実施例及び比較例の歯科用色調調整材組成物を充填し、カミソリ刃で余剰分を取り除き表面を平滑にし、技工用照射器αライトIII(モリタ社製)で90秒間光照射し重合させた。色差計(日本電色工業社製「SE6000」)を用い、光源をD65/2光源として試験前の試験片の色調を測定した。
試験片を99.5wt%のエタノールに室温で24hr浸漬後、2wt%のコーヒー水溶液に浸漬し直し、37℃で3日保存した。試験片を取り出し、流水で軽く洗い、弱エアーで試験片を乾燥させた。色差計にて試験後の試験片の色調を測色した。
試験前後の色調差(ΔE*)を求め、コーヒー変着色の指標とした。試験前の色度をL*1、a*1、b*1とした。試験後の色度をL*2、a*2、b*2とした。下記の式にて、色差(ΔE*)を算出した。ΔE=6以下が好ましく、ΔE=5以下が更に好ましい。
ΔE*=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)0.5
幅20×長さ30×厚み2mmの金型に歯冠用硬質レジン:エステニアC&B(E4 クラレノリタケデンタル社製)を充填し、技工用照射器「αライトIII」で表裏を180秒ずつ光照射し、硬化物を得た。硬化物表面を#3000耐水研磨紙で研磨した後、更に3μmのダイヤモンドペーストでバフ研磨し鏡面研磨面を得た。研磨面中央部に10mm四角範囲をカーボランダムを用いて粗造面を作製した。粗造面に各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、各実施例及び比較例の歯科用色調調整材組成物を塗布し、技工用照射器αライトIII(モリタ社製)で180秒間光照射し重合させた。色差計(日本電色工業社製「SE6000」)を用い、光源をD65/2光源として試験前の試験片中央部(組成物塗布面)の色調を測定した。
その後、歯磨き粉(ライオン社製、商品名「White&White」)40重量%と蒸留水60重量%のスラリーを調整し、スラリー中にて表面層の表面に歯ブラシ(ライオン社製、商品名「ビトイーン」、硬度ふつう)の毛を直に接触させ、250gの荷重をかけた状態で歯ブラシを振り幅10cmで4万回往復滑走させた。再度、試験後の試験片中央部(組成物塗布面)の色調を測定した。
試験前の色度をL*1、a*1、b*1とした。試験後の色度をL*2、a*2、b*2とした。下記の式にて、色差(ΔE*)を算出した。ΔE=6以下が好ましく、ΔE=5以下が更に好ましい。
ΔE*=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)0.5
幅20×長さ30×厚み2mmの金型に歯冠用硬質レジン:エステニアC&B(E4 クラレノリタケデンタル社製)を充填し、技工用照射器「ライトIII(モリタ社製)で表裏を180秒ずつ光照射し、硬化物を得た。硬化物表面を#3000耐水研磨紙で研磨した後、更に3μmのダイヤモンドペーストでバフ研磨し鏡面研磨面を得た。研磨面中央部に10mm四角範囲をカーボランダムを用いて粗造面を作製した。粗造面に各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、各実施例及び比較例の歯科用色調調整材組成物を塗布し、技工用照射器αライトIII(モリタ社製)で180秒間光照射し重合させた。歯磨き粉(ライオン社製、商品名「White&White」)40重量%と蒸留水60重量%のスラリーを調整し、スラリー中にて表面層の表面に歯ブラシ(ライオン社製、商品名「ビトイーン」、硬度ふつう)の毛を直に接触させ、250gの荷重をかけた状態で歯ブラシを振り幅10cmで4万回往復滑走させた。その後この面の光沢を、光沢度計(日本電色社製「VG2000」)を用い、鏡を100%としたときの割合(光沢度)で示した。測定の角度は60度とした。光沢度(滑沢耐久性)は、40%以上が好ましく、45%以上がより好ましく、55%以上が更に好ましい。
各実施例及び比較例の歯科用色調調整材組成物を0.6cc採取し、その23℃における粘度を、E型粘度計(東京計器製、VISCONICED)を用いて測定した。
Ф15×1mmの金型に歯冠用硬質レジン:エステニアC&B(E4 クラレノリタケデンタル社製)を充填し、技工用照射器αライトIII(モリタ社製)で180秒間光照射し重合させ、硬化板を作製した。作製した硬化板を色度板1とし、色調を測定した。色度板1に各実施例及び比較例のプライマー組成物を塗布し、表面をエアブローすることで、塗布したプライマーの流動性が無くなるまで乾燥した。次いで、各実施例及び比較例の歯科用色調調整材組成物を50μmの厚みで塗布し、技工用照射器αライトIII(モリタ社製)で180秒間光照射し重合させた。得られた硬化物を色度板2とした。色度板1と色度板2を色差計(日本電色社製「SE6000」)を用い、光源をD65/2光源とし、試験片の背後に標準白色板を置いて色度(Lab)を測定した。各実施例及び比較例の歯科用色調調整材組成物の厚みを、80μm、130μmとした以外は、上記と同様の方法で色度板を作製し、色度を測定した。色度板1の色度をL1、a1、b1とした。色度板2の色度をL2、a2、b2とした。下記の式にて、色差(ΔE)を算出した。
ΔE=((L1-L2)2+(a1-a2)2+(b1-b2)2)0.5
色調調整材の塗布厚みをX値、ΔEをY値とし、線形回帰直線の傾きを算出する。傾きが0.1以下であり、また、0より大きい値となるものが好ましい。
各実施例及び比較例の歯科用色調調整材組成物を50mlのスクリュー管瓶(アズワン社製)に40ml入れた後、スタティックミキサーで30秒間、激しく撹拌した。その後、室温にて1時間静置した。静置後、目視にて容器底部の沈降物の有無を目視にて確認した。沈降物が確認された時は×、沈降が認められなかった時は、○と判断した。
Claims (5)
- プライマー組成物(A)と歯科用色調調整材(B)とを含む歯科用色調調整材キットであって、
前記プライマー組成物(A)は、酸性基含有重合性単量体(a)と揮発性有機溶剤(b)とを含有し、
前記歯科用色調調整材(B)は、重合性単量体(d)、重合開始剤(e)、集塊粒子(f)、二酸化チタン(g)及び顔料(h)を含有し、
前記酸性基含有重合性単量体(a)の含有量は、前記プライマー組成物(A)の全重量の0.05~45重量%の範囲にあり、
前記揮発性有機溶剤(b)の含有量は、前記プライマー組成物(A)の全重量の55~99.95重量%の範囲にあり、
前記重合性単量体(d)は、1分子中に3個以上のアクリロイル基を持つ多官能アクリレート単量体(d1)と揮発性単官能(メタ)アクリレート単量体(d2)とを含有し、
前記単量体(d1)と前記単量体(d2)の合計量は、前記重合性単量体(d)の重量に対し88重量%以上であり、
前記集塊粒子(f)は、平均一次粒子径が1~50nmである超微粒子フィラーの鎖状の集塊粒子であり、
前記集塊粒子(f)の含有量は、前記重合性単量体(d)と前記集塊粒子(f)との合計重量100重量部に対し5~20重量部の範囲にあり、
前記二酸化チタン(g)の含有量は、前記重合性単量体(d)と前記集塊粒子(f)との合計重量100重量部に対し0.05~2重量部の範囲にあり、
前記顔料(h)は、前記二酸化チタン(g)を除く顔料である、
歯科用色調調整材キット。 - 前記プライマー組成物(A)がシランカップリング剤(c)を更に含有し、前記プライマー組成物(A)の組成が、
前記酸性基含有重量性単量体(a):0.05~40重量%、
前記揮発性有機溶剤(b):55~99.9重量%、
前記シランカップリング剤(c):0.01~40重量%、
である請求項1記載の歯科用色調調整材キット。 - 前記プライマー組成物(A)が水を含有しない、
請求項1又は2に記載の歯科用色調調整材キット。 - 前記歯科用色調調整材(B)の23℃における粘度が20~500mPa・sである、請求項1に記載の歯科用色調調整材キット。
- 請求項1に記載の歯科用色調調整材キットからなる歯科修復材用色調調整材キット。
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US15/033,193 US9675527B2 (en) | 2013-10-31 | 2014-10-28 | Dental color tone adjustment material kit |
EP14857644.0A EP3064194B1 (en) | 2013-10-31 | 2014-10-28 | Dental color tone adjustment material kit |
JP2015544802A JP6294341B2 (ja) | 2013-10-31 | 2014-10-28 | 歯科用色調調整材キット |
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