WO2017199925A1 - Composition de résine dentaire - Google Patents

Composition de résine dentaire Download PDF

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Publication number
WO2017199925A1
WO2017199925A1 PCT/JP2017/018253 JP2017018253W WO2017199925A1 WO 2017199925 A1 WO2017199925 A1 WO 2017199925A1 JP 2017018253 W JP2017018253 W JP 2017018253W WO 2017199925 A1 WO2017199925 A1 WO 2017199925A1
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WO
WIPO (PCT)
Prior art keywords
fibrous filler
resin composition
polycarbonate
dental resin
dental
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PCT/JP2017/018253
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English (en)
Japanese (ja)
Inventor
鈴木　憲司
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クラレノリタケデンタル株式会社
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Application filed by クラレノリタケデンタル株式会社 filed Critical クラレノリタケデンタル株式会社
Priority to JP2018518293A priority Critical patent/JP6971225B2/ja
Publication of WO2017199925A1 publication Critical patent/WO2017199925A1/fr

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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

Definitions

  • the present invention relates to a dental resin composition having high bending strength, flexural modulus, and toughness of a molded body, and having a good surface property of the molded body, and a method for producing the dental resin composition.
  • polycarbonate is used as a raw material for denture base materials, orthodontic brackets, artificial teeth, and the like.
  • Polycarbonate is extremely excellent in transparency and toughness, but has a problem that it is not high in strength or elastic modulus and easily deforms.
  • Patent Document 1 reports an example in which a polycarbonate having an isosorbide skeleton, which is excellent in strength, is applied to a dental molded body, compared to a conventional polycarbonate having a bisphenol skeleton.
  • Patent Document 1 has not reached a strength equivalent to that of dental materials made of metal, ceramic, and composite resin, leaving room for improvement in strength. .
  • an object of the present invention is to provide a dental resin composition having a molded article having high bending strength, flexural modulus and toughness, and having a good surface property of the molded article, and a method for producing the dental resin composition.
  • the present invention includes a polycarbonate (a) containing 15 to 98 mol% of a carbonate unit (A) represented by the following formula (A), and a fibrous filler (b),
  • a dental resin composition in which the fibrous filler (b) has a length of 0.5 to 10 mm and an aspect ratio of 100 to 10,000.
  • a dental resin composition in which the polycarbonate (a) includes a carbonate unit (B) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound is preferable.
  • the molar ratio ((A) / (B)) of a carbonate unit (A) and a carbonate unit (B) is preferable.
  • a dental resin composition having a content of the polycarbonate (a) of 40 to 99% by weight is preferred.
  • a dental resin composition in which the fibrous filler (b) is an inorganic fibrous filler (b1) and the aspect ratio of the inorganic fibrous filler (b1) is 205 to 7500 is preferable.
  • a dental resin composition in which the fibrous filler (b) is an organic fibrous filler (b2) and the aspect ratio of the organic fibrous filler (b2) is 1000 to 10,000 is preferable.
  • the present invention provides a method for producing a dental resin composition, comprising a polycarbonate unit (a) containing 15 mol% or more and 98 mol% or less of a carbonate unit (A) represented by the above formula (A). And a fibrous filler (b) are mixed, the length of the fibrous filler (b) is 0.5 to 10 mm, and the aspect ratio is 100 to 10,000.
  • a production method in which the mixing step includes a melt-kneading step is preferable.
  • a dental resin composition produced by any of the production methods described above is preferred.
  • the dental molded body is preferably a denture base.
  • the dental resin composition of the present invention has high bending strength, flexural modulus and toughness of the molded body, and the surface properties of the molded body are good. Moreover, according to the manufacturing method of the dental resin composition of this invention, the said dental resin composition can be manufactured efficiently. Furthermore, the dental resin composition of the present invention is particularly useful for denture bases.
  • the dental resin composition according to one aspect of the present invention includes a polycarbonate (a) containing 15 to 98 mol% of a carbonate unit (A) represented by the above formula (A), a fibrous filler (b), and The fibrous filler (b) has a length of 0.5 to 10 mm and an aspect ratio of 100 to 10,000. Thereby, the bending strength, bending elastic modulus, and toughness of the molded body are high, and the dental resin composition has a good surface property.
  • the carbonate unit (A) contained in a predetermined amount in the polycarbonate (a) is a stereoselective, bulky and rigid ring structure. Expressing high strength, reducing the difference in strength from the fibrous filler (b), and the ether structure with a cyclic conformation fixed to the fibrous filler (b) has an affinity for the polycarbonate ( It is estimated that a) and the fibrous filler (b) can be integrated.
  • Polycarbonate (a) Polycarbonate (a) is used as a base material in the dental resin composition of the present invention because it is excellent in toughness and affinity with a dental adhesive.
  • the polycarbonate (a) includes a carbonate unit (A) represented by the above formula (A).
  • the content of the carbonate unit (A) is from 15 mol% to 98 mol% in all carbonate units, preferably from 30 mol% to 95 mol%, more preferably from 50 mol% to 90 mol%.
  • the upper limit value and the lower limit value of the numerical ranges content of each component, fiber length, values calculated from each component, physical properties, etc.
  • Carbonate unit (A) The carbonate unit (A) according to the present invention is derived from an alicyclic diol compound having an ether group, as shown in the formula (A).
  • Examples of the carbonate unit (A) include repeating units (A1), (A2) and (A3) represented by the following formulas having a stereoisomeric relationship.
  • the alicyclic diol compound constituting these repeating units is a saccharide-derived ether diol, which is obtained from natural biomass, and is one of the so-called renewable resources.
  • the alicyclic diol compounds constituting the repeating units (A1), (A2) and (A3) are isosorbide (1,4; 3,6-dianhydro-D-sorbitol) and isomannide (1,4; 3,6), respectively.
  • Isosorbide can be obtained by hydrogenating D-glucose obtained from starch and then dehydrating it.
  • ether diols can be obtained by the same reaction except for the starting materials.
  • isosorbide, isomannide, and isoidide a repeating unit derived from isosorbide is particularly preferable because it is easy to manufacture and has excellent heat resistance, and is not easily deteriorated during processing.
  • the polycarbonate (a) is preferably a copolymer further containing the following carbonate unit (B).
  • the carbonate unit (B) in the polycarbonate (a) of the present invention is derived from at least one compound (diol component) selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound.
  • the content of the carbonate unit (B) is preferably from 2 mol% to 75 mol%, more preferably from 5 mol% to 70 mol%, and still more preferably from 10 mol% to 50 mol% in all carbonate units.
  • the aliphatic diol compound may be either a linear aliphatic diol compound or a branched aliphatic diol compound.
  • the number of carbon atoms of the linear aliphatic diol compound is preferably 2 to 30, more preferably 4 to 20, and still more preferably 6 to 18.
  • the carbon number of the branched chain aliphatic diol compound is preferably 3 to 30, more preferably 3 to 20, and still more preferably 4 to 12.
  • the number of carbon atoms in the alicyclic diol compound is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15.
  • linear aliphatic diol compound examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,18-octadecanediol and the like.
  • 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable.
  • branched aliphatic diol compound examples include 1,3-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n- Butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2- Octyl glycol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3-diisobutyl-1,3- Examples include propanediol, 2,2-diisoamyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propan
  • 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol is preferred.
  • alicyclic diol compound examples include alicyclic diol compounds other than the alicyclic diol compound capable of inducing the carbonate unit (A) such as isosorbide.
  • Specific examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol; , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol; norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol,
  • aliphatic diol compounds and alicyclic diol compounds constituting the carbonate unit (B) may be used alone or in combination of two or more.
  • the diol component used by this invention may use together an aliphatic diol compound and / or an alicyclic diol compound, and an aromatic diol compound in the range which does not impair the effect of this invention.
  • Aromatic diol compounds include 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, , 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, , 2'-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl)- 1,1,1,3,3,3-hexafluoropropane (bisphenol AF) and 1,1-bis (4-hydro) Shifeniru) decane, and the like.
  • the polycarbonate (a) used in the present invention preferably contains a carbonate unit (A) and further contains a carbonate unit (B).
  • the molar ratio (A) / (B) between these carbonate units (A) and carbonate units (B) is preferably 15/85 to 95/5.
  • the molar ratio (A) / (B) is more preferably 30/70 to 90/10, further preferably 40/60 to 90/10, particularly preferably 50/50 to 90/10, and most preferably 60/40. ⁇ 90/10.
  • the molar ratio of each repeating unit is, for example, a high-resolution Fourier transform nuclear magnetic resonance apparatus (FT-NMR) (model: JNM-AL400, manufactured by JEOL Ltd.) or a Fourier transform nuclear magnetic resonance apparatus (FT-NMR) (model). : JNM-ECX400 (manufactured by JEOL Ltd.), the polycarbonate (a) can be measured and calculated by 1 H-NMR.
  • FT-NMR high-resolution Fourier transform nuclear magnetic resonance apparatus
  • FT-NMR Fourier transform nuclear magnetic resonance apparatus
  • the total content of the carbonate unit (A) and the carbonate unit (B) is preferably 70 mol% or more, more preferably 80 mol% or more in the total carbonate units. More preferably, it is more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 98 mol% or more.
  • the total content of the carbonate unit (A) and the carbonate unit (B) in the polycarbonate (a) The amount may be 100 mol%.
  • the content of the polycarbonate (a) used in the present invention in the dental resin composition is preferably 40% by weight or more, more preferably 50% by weight or more, and 60% by weight or more. Is more preferable.
  • the content of the polycarbonate (a) in the dental resin composition is preferably 99% by weight or less, more preferably 95% by weight or less, and further preferably 90% by weight or less. It is particularly preferably 80% by weight or less, and most preferably 70% by weight or less.
  • the content of the polycarbonate (a) in the dental resin composition is 40 to 99% by weight, the strength can be improved without impairing the transparency and toughness.
  • the polycarbonate (a) used in the present invention is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method in which a diol component is reacted (ester exchange reaction) with a carbonate precursor (carbonic acid diester, etc.). Is done. Next, these manufacturing methods will be briefly described.
  • the transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of a diol component is stirred with a carbonic acid diester in an inert gas atmosphere while distilling off the alcohol or phenol produced.
  • the reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C.
  • the reaction is preferably completed by distilling off the alcohol or phenol produced by reducing the pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.
  • Examples of the carbonic acid diester used in the transesterification include esters such as an optionally substituted aryl group having 6 to 12 carbon atoms and an optionally substituted aralkyl group having 7 to 13 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred.
  • the amount of carbonic acid diester to be used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, relative to 1 mol of the diol component in total.
  • a polymerization catalyst can be used to increase the polymerization rate.
  • the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, nitrogen-containing compounds, metal compounds and the like.
  • organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, and the like of alkali metals or alkaline earth metals are preferably used.
  • These compounds may be used individually by 1 type, and may use 2 or more types together.
  • alkali metal compound examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, acetic acid.
  • alkaline earth metal compound examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, Examples include strontium hydrogen carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate.
  • Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl.
  • Alkali metal salts or alkaline earth metal salts such as boron, tributylphenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, butyl triphenyl boron , Magnesium salt, or strontium salt).
  • Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
  • nitrogen-containing compound examples include quaternary ammonium hydroxy having an alkyl group or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Dos.
  • nitrogen-containing compounds include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole.
  • examples of the nitrogen-containing compound include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, and the like.
  • the metal compound examples include a zinc aluminum compound, a germanium compound, an organic tin compound, an antimony compound, a manganese compound, a titanium compound, and a zirconium compound.
  • the amount of these polymerization catalysts used is preferably in the range of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 2 equivalent, more preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 5 per mole of the diol component.
  • the range is equivalent, and more preferably in the range of 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 3 equivalents.
  • a catalyst deactivator can be added in the late stage of reaction (at a temperature in the vicinity (Tg + 10 ° C.) near the glass transition temperature of polycarbonate (about 100 ° C. to 150 ° C.)).
  • known catalyst deactivators are effectively used. Among them, sulfonic acid ammonium salts, sulfonic acid phosphonium salts, and sulfonic acid esters are preferable.
  • salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid; salts of p-toluenesulfonic acid such as p-toluenesulfonic acid tetrabutylammonium salt are preferable.
  • sulfonate ester examples include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p -Butyl toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, etc. are preferably used.
  • dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.
  • the amount of the catalyst deactivator used is such that when at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, a ratio of 0.5 to 50 mol per mol of the polymerization catalyst is used. A ratio of 0.5 to 10 mol is more preferable, and a ratio of 0.8 to 5 mol is more preferable.
  • Fibrous filler (b) The dental resin composition of the present invention is blended with a fibrous filler (b) having a length of 0.5 to 10 mm and an aspect ratio of 100 to 10,000 in order to improve strength and elastic modulus.
  • a fibrous filler (b) examples include inorganic fibrous filler (b1) and organic fibrous filler (b2).
  • Examples of the material of the inorganic fibrous filler (b1) include silica; quartz fiber, glass fiber (chopped strand), glass wool, and the like. These can be used alone or in combination of two or more.
  • Examples of the material for the organic fibrous filler (b2) include cellulose, chitin, chitosan, polyether ether ketone, polyether ketone ketone, polyimide, polyamide, nylon, polyester, polyarylate, polycarbonate, polyphenylene ether, polyoxymethylene, Examples include polyethylene. These can be used alone or in combination of two or more. Among these, cellulose, polyether ether ketone, polyether ketone ketone, polyimide, and polyamide are preferable from the viewpoint of strength.
  • the inorganic fibrous filler (b1) may be used after being surface-treated with a known surface treatment material as necessary.
  • the surface treatment material include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol; alkanolamines such as triethylamine; organosilicone compounds such as organopolysiloxane; higher fatty acids such as stearic acid (12 or more carbon atoms) 24 or less); fatty acid metal salts such as calcium stearate and magnesium stearate (carbon number 12 to 24); hydrocarbon lubricants such as polyethylene wax and liquid paraffin; basic amino acids such as lysine and arginine; polyglycerin and its derivatives
  • the surface treatment material is selected from the group consisting of alcohols, alkanolamines, organic silicone compounds, higher fatty acids, fatty acid metal salts, hydrocarbon lubricants, basic amino acids, polyglycerol and derivatives thereof, and coupling agents. 1 type or more is mentioned.
  • the length (fiber length) of the fibrous filler (b) is 0.5 to 10 mm. This length is preferably 7.5 mm or less, more preferably 5.0 mm or less, from the viewpoints of not producing transparency and a pattern when dispersed in the polycarbonate (a) and not causing anisotropy in the molded product. Further, the length is preferably 1.0 mm or more, and more preferably 1.5 mm or more from the viewpoint of exhibiting a sufficient reinforcing effect. Furthermore, the aspect ratio of the fibrous filler (b) is 100 to 10,000, preferably 205 to 7500, and more preferably 250 to 5000. The aspect ratio here is a value obtained by dividing the fiber length ( ⁇ m) by the fiber diameter ( ⁇ m).
  • the aspect ratio of the fibrous filler can be determined by observation with an optical microscope or an electron microscope.
  • an optical microscope is simple for measuring a fiber diameter of a fiber diameter of 0.10 ⁇ m or more
  • an electron microscope observation is simple for measuring a fiber diameter of a fiber having a fiber diameter of less than 0.10 ⁇ m.
  • the length is preferably 1.0 to 7.5 mm, more preferably 1.5 to 5.0 mm.
  • the aspect ratio of the inorganic fibrous filler (b1) is preferably 205 to 7500, more preferably 210 to 5000, further preferably 210 to 3000, and preferably 215 to 2000. Particularly preferred.
  • the fiber diameter is preferably 0.10 to 20.0 ⁇ m, more preferably 1.0 to 18.0 ⁇ m, and further preferably 5.0 to 18.0 ⁇ m. Moreover, 10.0 micrometers or more may be sufficient.
  • the length is preferably 1.0 to 7.5 mm, more preferably 1.5 to 5.0 mm.
  • the aspect ratio of the organic fibrous filler (b2) is preferably 1000 to 10,000, more preferably 2000 to 10,000, still more preferably 3000 to 9800, and more preferably 3500 to 9500. Particularly preferred.
  • the fiber diameter is preferably 0.05 to 3.0 ⁇ m, more preferably 0.10 to 2.0 ⁇ m.
  • the blending amount of the fibrous filler (b) is not particularly limited, but is preferably 1% by weight or more in the dental resin composition from the viewpoint of processability and the strength of the dental resin composition, and is 5% by weight or more. More preferably, it is more preferably 10% by weight or more, particularly preferably 20% by weight or more, and most preferably 30% by weight or more.
  • the blending amount of the fibrous filler (b) is preferably 60% by weight or less, more preferably 50% by weight or less, and 40% by weight from the viewpoint that workability and toughness are kept good. More preferably, it is as follows. The strength of the dental resin composition obtained when the content of the fibrous filler (b) is 1% by weight or more is kept good, and the processability of the dental resin composition obtained when it is 60% by weight or less, Good toughness is maintained.
  • fibrous filler (b) Commercial products can be used as the fibrous filler (b). Examples of such commercially available products include CS chopped strand (manufactured by Nitto Boseki Co., Ltd.), cellulose nanofiber (manufactured by Sugino Machine Co., Ltd.), aramid fiber (meta-aramid fiber, para-aramid fiber; manufactured by Toray DuPont) ) And the like.
  • a filler other than the fibrous filler (b) may be blended for the purpose of adjusting mechanical performance and the like within a range not impairing the object of the present invention.
  • fillers other than the fibrous filler (b) include plate-like fillers, spherical fillers, and crushed fillers. These plate-like filler, spherical filler and crushed filler may be organic fillers and / or inorganic fillers or organic-inorganic composite fillers. These are preferably such that the total amount of the fibrous filler (b) does not exceed 60% by weight, more preferably does not exceed 45% by weight, and exceeds 40% by weight in the dental resin composition of the present invention. More preferably not.
  • the dental resin composition of the present invention can be blended with known additives within a range that does not deteriorate the performance.
  • additives include antioxidants, colorants (pigments, dyes, fibers, etc.), ultraviolet absorbers, organic solvents, thickeners, and the like.
  • a denture base with a transparent feeling can be obtained using a resin composition containing a colorant.
  • the amount of these additives is not particularly limited, but may be less than 10% by weight, less than 5.0% by weight, less than 1.0% by weight, It may be less than 3% by weight.
  • the dental resin composition of this invention can be manufactured by mixing the said polycarbonate (a) and the said fibrous filler (b). it can.
  • This invention is a manufacturing method of a dental resin composition, Comprising: The polycarbonate (a) and fibrous filler (b) which contain the carbonate unit (A) represented by the said Formula (A) 15 mol% or more and 98 mol% or less And a manufacturing method in which the length of the fibrous filler (b) is 0.5 to 10 mm and the aspect ratio is 100 to 10,000.
  • the dental resin composition described above can be produced by the production method.
  • the dental resin composition manufactured by the manufacturing method of this invention satisfy
  • a known mixing method such as a method of melt-kneading the filler (b) and, if necessary, a filler other than the fibrous filler (b) and, if necessary, an additive, etc.
  • melt-kneading with a twin screw extruder or the like
  • a method including a step of melt-kneading the polycarbonate (a) and the fibrous filler (b) is preferable.
  • the most preferred method is melt kneading with a twin screw extruder.
  • the temperature at the time of melt-kneading may be about 130 to 350 ° C., for example.
  • Examples of uses of the molded body of the dental resin composition of the present invention include denture bases, orthodontic brackets, and artificial teeth.
  • the denture base is generally colored in clear or gingival color, and includes a denture base of a complete denture, a denture base of a partial denture, and the like and supports an artificial tooth and functions as a mounting portion in the oral cavity. More specifically, a denture base of a base denture (non-clasp denture) that basically does not use a wire (clasp) or metal, a denture base of a partial denture having a wire clasp, and further, a denture base of the above-mentioned complete denture including.
  • Artificial teeth include those that are integrated with the denture base to constitute dentures, those that are directly implanted in the oral cavity, and the like.
  • the molding method of the dental resin composition of the present invention is not particularly limited.
  • a method for obtaining a denture base, a bracket or the like from a pellet by injection molding, or a pellet is once molded by injection molding.
  • a known forming method such as a method of cutting using a CAD / CAM system or a method of extruding a pellet from a pellet using a 3D printing system and laminating and forming can be used.
  • the most preferred method is injection molding or cutting with a CAD / CAM system.
  • 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.
  • the reaction was carried out with stirring for a total of 6 hours, discharged from the bottom of the reaction tank under nitrogen pressure, and cut with a pelletizer while cooling in a water tank to obtain a pellet.
  • the ISS / HD (molar ratio) of the polycarbonate (a) -1 was 75/25.
  • GF1 Glass fiber (trade name: CS chopped strand CS 3 PE-455S, manufactured by Nitto Boseki Co., Ltd., fiber length: 3.0 mm, aspect ratio: 230, silane surface treatment)
  • GF2 Glass fiber (trade name: CS chopped strand CS 3.8 J-455S, manufactured by Nitto Boseki Co., Ltd., fiber length: 3.8 mm, aspect ratio: 350, silane surface treatment)
  • CNF Cellulose nanofiber (Brand name: BiNFi-s, manufactured by Sugino Machine Co., Ltd., fiber length 1.7 mm, aspect ratio 9500)
  • PA Para-aramid fiber (trade name: Kevlar, manufactured by Toray Industries, Inc., fiber length 4.5 mm, aspect ratio 4500)
  • Examples 1 to 9 and Comparative Examples 1 to 7 (1) The above-described components were premixed in the proportions (parts by weight) shown in Tables 1 and 2 below, and then collectively mixed with a twin-screw extruder [KZW15-45MG manufactured by Technobel Co., Ltd., shaft diameter ⁇ 15 mm L / D45 The mixture was melt-kneaded at a temperature of 240 to 300 ° C. and a rotation speed of 300 rpm, extruded into a strand shape, and cut with a strand cutter to produce a pellet of a dental resin composition.
  • a twin-screw extruder KZW15-45MG manufactured by Technobel Co., Ltd., shaft diameter ⁇ 15 mm L / D45
  • the bending strength of the molded body is preferably 150 MPa or more, more preferably 170 MPa or more, and further preferably 175 MPa or more.
  • the flexural modulus of the molded body is preferably 3500 MPa or more, more preferably 3900 MPa or more, and further preferably 4000 MPa or more.
  • ⁇ Toughness evaluation (total fracture work)> A test piece having a thickness of 8.0 mm, a width of 3.0 mm, a length of 39 mm, and a notch depth of 3.0 mm was cut out from each disk obtained in Examples and Comparative Examples. About the obtained test piece, the fracture toughness test was done based on JIST6501: 2012, and the total fracture work was evaluated. If the total fracture work is a value exceeding 4.0 kJ / m 2 , the molded article is excellent in toughness, and preferably 5.0 kJ / m 2 or more.
  • the average value of the measured values at five locations on the test piece was used as an index of surface properties (smoothness).
  • Rp is preferably 150 ⁇ m or less, and more preferably 100 ⁇ m or less, from the viewpoint that it is less likely to feel discomfort such as a tingling sensation when used in the oral cavity. Furthermore, the presence or absence of the stripe pattern was visually observed about the test piece cut out from the test piece of the fracture toughness test as mentioned above.
  • the dental resin composition of the present invention has high bending strength, bending elastic modulus and toughness of the obtained molded article, has no striped pattern, has excellent appearance, has high smoothness, and feels good to use. It was confirmed that it was excellent.
  • the composition of Comparative Example 1 in which no fibrous filler is blended, and the compositions of Comparative Examples 2 and 3 in which a short length of fibrous filler is blended are the bending strength and flexural modulus of the resulting molded body. And the compositions of Comparative Examples 2 and 3 also had low toughness.
  • composition of Comparative Example 4 in which a fibrous filler having a long fiber length was blended had a rough polished surface and a striped pattern, and the surface properties were poor. Furthermore, the compositions of Comparative Examples 5 and 6 using bisphenol-based polycarbonate had low bending strength of the resulting molded articles, and the polished surface was rougher than in the examples.
  • the polycarbonate (a) and the fibrous filler (b) are used in combination, thereby bending. It can be seen that the strength and surface properties are synergistically improved.
  • the dental resin composition of the present invention has high bending strength, flexural modulus and toughness of the molded body, and has good surface properties, and is particularly useful for denture bases.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine dentaire dont un produit moulé à partir de cette dernière présente une résistance à la flexion élevée, un module de flexion élevé et une ténacité élevée et présente de bonnes propriétés de surface, ainsi qu'un procédé de fabrication de la composition de résine dentaire. La présente invention concerne : une composition de résine dentaire comprenant un polycarbonate (a), qui contient entre 15 et 98 % en moles, inclus, d'une unité carbonate (A) représentée par la formule (A), et un élément de charge fibreux (b), la longueur de l'élément de charge fibreux (b) étant comprise entre 0,5 et 10 mm et le rapport de forme de ce dernier étant compris entre 100 et 10 000 ; et un procédé de fabrication d'une composition de résine dentaire, ledit procédé comprenant une étape de mélange du polycarbonate (a), qui contient entre 15 et 98 % en moles, inclus, de l'unité carbonate (A) représentée par la formule (A), avec un élément de charge fibreux (b), la longueur de l'élément de charge fibreux (b) étant comprise entre 0,5 et 10 mm et le rapport de forme de ce dernier étant compris entre 100 et 10 000.
PCT/JP2017/018253 2016-05-19 2017-05-15 Composition de résine dentaire WO2017199925A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200100556A (ko) * 2019-02-18 2020-08-26 라인치과기공주식회사 치과용 보철 조성물
JP2020193299A (ja) * 2019-05-30 2020-12-03 株式会社トクヤマデンタル 親水化表面処理剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009541568A (ja) * 2006-06-30 2009-11-26 スティック テック オサケユイチア 繊維−補強複合体およびその製造方法
JP2013535532A (ja) * 2010-07-14 2013-09-12 ザ・キュレーターズ・オブ・ザ・ユニバーシティ・オブ・ミズーリ ポリマー複合体およびその作製
JP2014161547A (ja) * 2013-02-26 2014-09-08 Teijin Ltd 歯科用成形体

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001002906A (ja) * 1999-06-18 2001-01-09 Shikoku Chem Corp 安定化ポリカーボネート樹脂組成物
US7728059B2 (en) * 2006-02-14 2010-06-01 Sabic Innovative Plastics Ip B.V. Polycarbonate compositions and articles formed therefrom
JP2011110388A (ja) * 2009-11-24 2011-06-09 Catalymedic Inc 複合生体材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009541568A (ja) * 2006-06-30 2009-11-26 スティック テック オサケユイチア 繊維−補強複合体およびその製造方法
JP2013535532A (ja) * 2010-07-14 2013-09-12 ザ・キュレーターズ・オブ・ザ・ユニバーシティ・オブ・ミズーリ ポリマー複合体およびその作製
JP2014161547A (ja) * 2013-02-26 2014-09-08 Teijin Ltd 歯科用成形体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200100556A (ko) * 2019-02-18 2020-08-26 라인치과기공주식회사 치과용 보철 조성물
KR102384593B1 (ko) * 2019-02-18 2022-04-08 라인치과기공주식회사 치과용 보철 조성물
JP2020193299A (ja) * 2019-05-30 2020-12-03 株式会社トクヤマデンタル 親水化表面処理剤
JP7168936B2 (ja) 2019-05-30 2022-11-10 株式会社トクヤマデンタル 親水化表面処理剤

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