WO2017199925A1 - Dental resin composition - Google Patents
Dental resin composition Download PDFInfo
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- 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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- Prior art keywords
- fibrous filler
- resin composition
- polycarbonate
- dental resin
- dental
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- 0 CCC*(C)OC(CO[C@@]12)[C@]1OCC2OC(*CC1CC1)=O Chemical compound CCC*(C)OC(CO[C@@]12)[C@]1OCC2OC(*CC1CC1)=O 0.000 description 1
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
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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided are a dental resin composition, a molded product of which shows a high flexural strength, a high flexural modulus and a high toughness and has good surface properties, and a method for manufacturing the dental resin composition. The present invention relates to: a dental resin composition comprising a polycarbonate (a), which contains 15-98 mol% inclusive of a carbonate unit (A) represented by formula (A), and a fibrous filler (b), wherein the length of the fibrous filler (b) is 0.5-10 mm and the aspect ratio thereof is 100-10,000; and a method for manufacturing a dental resin composition, said method comprising a step for mixing a polycarbonate (a), which contains 15-98 mol% inclusive of a carbonate unit (A) represented by formula (A), with a fibrous filler (b), wherein the length of the fibrous filler (b) is 0.5-10 mm and the aspect ratio thereof is 100-10,000.
Description
本発明は、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好な歯科用樹脂組成物及びその製造方法に関する。
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.
従来、義歯床材料、矯正用ブラケット、人工歯等の原料としてポリカーボネートが使用されている。ポリカーボネートは透明性、靭性には極めて優れているが、強度若しくは弾性率が高くはなく、変形しやすいことが課題であった。
Conventionally, 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.
ポリカーボネートに限定されず、樹脂の強度若しくは弾性率を向上させる方法として、無機フィラー、ガラス繊維、又は炭素繊維を混合することが、工業的に広く応用されている。しかしながら、無機フィラーを配合した場合は成形体が脆くなる傾向があり、ガラス繊維を配合した場合は歯科材料として口腔内で使用した場合はチクチクとした感覚が生じたり、成形体の表面に波状の模様が浮き出て外観を損なうことがあり、力学的な物性に異方性が生じることがあり、炭素繊維を使用した場合は色調を損なう等、ポリカーボネートの特長を失ったり、口腔内で使用するには課題があった。
It is not limited to polycarbonate, and as a method for improving the strength or elastic modulus of a resin, mixing an inorganic filler, glass fiber, or carbon fiber is widely applied industrially. However, when an inorganic filler is blended, the molded product tends to become brittle. When glass fiber is blended, a tingling sensation occurs when used in the oral cavity as a dental material, or the surface of the molded product is wavy. Patterns may appear and the appearance may be impaired, anisotropy may occur in the mechanical properties, and if carbon fiber is used, the color tone may be impaired, and the characteristics of polycarbonate may be lost or used in the oral cavity. Had a challenge.
このような課題に対し、近年、新たな構造を有するポリカーボネートを開発するという試みがなされている。特許文献1には、従来のビスフェノール骨格を有するポリカーボネートに対し、イソソルビド骨格を有する強度に優れたポリカーボネートを歯科用成形体に応用した例が報告されている。
In response to such problems, attempts have been made in recent years to develop polycarbonate having a new structure. 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.
しかしながら、特許文献1の歯科用成形体は、金属製、セラミック製、及びコンポジットレジン製の歯科材料に相当するほどの強度には到達しておらず、強度には改善の余地が残されていた。
However, the dental molded body of 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. .
そこで、本発明は、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好な歯科用樹脂組成物及びその製造方法を提供することを目的とする。
Therefore, 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.
本発明は、ある側面において、下記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と、繊維状フィラー(b)とを含有し、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である歯科用樹脂組成物を提供する。
In one aspect, 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), Provided is 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.
さらに、前記ポリカーボネート(a)が、脂肪族ジオール化合物及び脂環式ジオール化合物からなる群より選ばれる少なくとも1種の化合物から誘導されるカーボネート単位(B)を含む歯科用樹脂組成物が好ましい。
Furthermore, 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.
前記ポリカーボネート(a)がカーボネート単位(B)を含む歯科用樹脂組成物における当該ポリカーボネート(a)において、カーボネート単位(A)とカーボネート単位(B)とのモル比((A)/(B))が、15/85~95/5である歯科用樹脂組成物が好ましい。
In the said polycarbonate (a) in the dental resin composition in which the said polycarbonate (a) contains a carbonate unit (B), the molar ratio ((A) / (B)) of a carbonate unit (A) and a carbonate unit (B) However, a dental resin composition having a ratio of 15/85 to 95/5 is preferable.
前記ポリカーボネート(a)の含有量が、40~99重量%である歯科用樹脂組成物が好ましい。
A dental resin composition having a content of the polycarbonate (a) of 40 to 99% by weight is preferred.
前記繊維状フィラー(b)が無機繊維状フィラー(b1)であり、前記無機繊維状フィラー(b1)のアスペクト比が205~7500である歯科用樹脂組成物が好ましい。
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.
前記繊維状フィラー(b)が有機繊維状フィラー(b2)であり、前記有機繊維状フィラー(b2)のアスペクト比が1000~10000である歯科用樹脂組成物が好ましい。
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.
また別の側面として、本発明は、歯科用樹脂組成物の製造方法であって、上記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と繊維状フィラー(b)とを混合する工程を含み、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である、製造方法を提供する。
As another aspect, 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.
前記混合する工程が溶融混練する工程を含む製造方法が好ましい。
A production method in which the mixing step includes a melt-kneading step is preferable.
前記したいずれかの製造方法によって製造される歯科用樹脂組成物が好ましい。
A dental resin composition produced by any of the production methods described above is preferred.
前記したいずれかの歯科用樹脂組成物からなる歯科用成形体であることが好ましい。
It is preferably a dental molded body made of any of the aforementioned dental resin compositions.
前記歯科用成形体は義歯床であることが好ましい。
The dental molded body is preferably a denture base.
本発明の歯科用樹脂組成物は、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好である。また、本発明の歯科用樹脂組成物の製造方法によれば前記歯科用樹脂組成物を効率よく製造することができる。さらに、本発明の歯科用樹脂組成物は、特に義歯床に有用である。
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.
以下、本発明を詳細に説明する。
本発明の一側面における歯科用樹脂組成物は、上記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と、繊維状フィラー(b)とを含有し、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である。これにより、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好な歯科用樹脂組成物となる。本発明の歯科用樹脂組成物によって当該効果が奏される理由は必ずしも定かではないが、ポリカーボネート(a)に所定量含まれるカーボネート単位(A)は、立体選択的で嵩高く剛直な環構造により高い強度を発現して繊維状フィラー(b)との強度差を小さくし、また、環状で立体配座が固定されたエーテル構造が繊維状フィラー(b)に対して親和し、これらによってポリカーボネート(a)と繊維状フィラー(b)とが一体化できるためと推測される。 Hereinafter, the present invention will be described in detail.
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 reason why the effect is exhibited by the dental resin composition of the present invention is not necessarily clear, but 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.
本発明の一側面における歯科用樹脂組成物は、上記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と、繊維状フィラー(b)とを含有し、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である。これにより、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好な歯科用樹脂組成物となる。本発明の歯科用樹脂組成物によって当該効果が奏される理由は必ずしも定かではないが、ポリカーボネート(a)に所定量含まれるカーボネート単位(A)は、立体選択的で嵩高く剛直な環構造により高い強度を発現して繊維状フィラー(b)との強度差を小さくし、また、環状で立体配座が固定されたエーテル構造が繊維状フィラー(b)に対して親和し、これらによってポリカーボネート(a)と繊維状フィラー(b)とが一体化できるためと推測される。 Hereinafter, the present invention will be described in detail.
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 reason why the effect is exhibited by the dental resin composition of the present invention is not necessarily clear, but 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.
ポリカーボネート(a)
ポリカーボネート(a)は、本発明の歯科用樹脂組成物において、靭性及び歯科用接着材との親和性に優れるため、基材として用いられる。ポリカーボネート(a)は、上記式(A)で表されるカーボネート単位(A)を含む。カーボネート単位(A)の含有量は、全カーボネート単位中15モル%以上98モル%以下であり、30モル%以上95モル%以下が好ましく、50モル%以上90モル%以下がより好ましい。なお、本明細書において、数値範囲(各成分の含有量、繊維長、各成分から算出される値及び各物性等)の上限値及び下限値は適宜組み合わせ可能である。 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%. In the present specification, 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.) can be appropriately combined.
ポリカーボネート(a)は、本発明の歯科用樹脂組成物において、靭性及び歯科用接着材との親和性に優れるため、基材として用いられる。ポリカーボネート(a)は、上記式(A)で表されるカーボネート単位(A)を含む。カーボネート単位(A)の含有量は、全カーボネート単位中15モル%以上98モル%以下であり、30モル%以上95モル%以下が好ましく、50モル%以上90モル%以下がより好ましい。なお、本明細書において、数値範囲(各成分の含有量、繊維長、各成分から算出される値及び各物性等)の上限値及び下限値は適宜組み合わせ可能である。 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%. In the present specification, 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.) can be appropriately combined.
カーボネート単位(A)
本発明にかかるカーボネート単位(A)は前記式(A)に示したように、エーテル基を有する脂環式ジオール化合物から誘導されるものである。前記カーボネート単位(A)としては、立体異性体の関係にある下記式で表される繰り返し単位(A1)、(A2)及び(A3)が例示される。 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.
本発明にかかるカーボネート単位(A)は前記式(A)に示したように、エーテル基を有する脂環式ジオール化合物から誘導されるものである。前記カーボネート単位(A)としては、立体異性体の関係にある下記式で表される繰り返し単位(A1)、(A2)及び(A3)が例示される。 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.
これらの繰り返し単位を構成する脂環式ジオール化合物は、糖質由来のエーテルジオールであり、自然界のバイオマスからも得られるもので、再生可能資源と呼ばれるものの1つである。繰り返し単位(A1)、(A2)及び(A3)を構成する脂環式ジオール化合物は、それぞれイソソルビド(1,4;3,6-ジアンヒドロ-D-ソルビトール)、イソマンニド(1,4;3,6-ジアンヒドロ-D-マンニトール)、イソイディッド(1,4:3,6-ジアンヒドロ-L-イジトール)と呼ばれる。イソソルビドは、デンプンから得られるD-グルコースに水添した後、脱水することにより得られる。その他のエーテルジオールについても、出発物質を除いて同様の反応により得られる。イソソルビド、イソマンニド、イソイディッドの中でも、特にイソソルビドから誘導される繰り返し単位が、製造の容易さ、耐熱性に優れるため加工時に劣化しにくいことから好ましい。
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. -Dianhydro-D-mannitol), isoidid (1,4: 3,6-dianhydro-L-iditol). Isosorbide can be obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials. Among 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.
カーボネート単位(B)
ポリカーボネート(a)は、下記カーボネート単位(B)をさらに含む共重合体であることが好ましい。本発明のポリカーボネート(a)におけるカーボネート単位(B)は、脂肪族ジオール化合物及び脂環式ジオール化合物からなる群より選ばれる少なくとも1種の化合物(ジオール成分)から誘導されるものである。カーボネート単位(B)の含有量は、全カーボネート単位中2モル%以上75モル%以下が好ましく、5モル%以上70モル%以下がより好ましく、10モル%以上50モル%以下がさらに好ましい。 Carbonate unit (B)
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.
ポリカーボネート(a)は、下記カーボネート単位(B)をさらに含む共重合体であることが好ましい。本発明のポリカーボネート(a)におけるカーボネート単位(B)は、脂肪族ジオール化合物及び脂環式ジオール化合物からなる群より選ばれる少なくとも1種の化合物(ジオール成分)から誘導されるものである。カーボネート単位(B)の含有量は、全カーボネート単位中2モル%以上75モル%以下が好ましく、5モル%以上70モル%以下がより好ましく、10モル%以上50モル%以下がさらに好ましい。 Carbonate unit (B)
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.
脂肪族ジオール化合物は、直鎖脂肪族ジオール化合物又は分岐鎖脂肪族ジオール化合物のいずれでもよい。直鎖脂肪族ジオール化合物の炭素数としては、2~30が好ましく、4~20がより好ましく、6~18がさらに好ましい。また、分岐鎖脂肪族ジオール化合物の炭素数としては、3~30が好ましく、3~20がより好ましく、4~12がさらに好ましい。脂環式ジオール化合物の炭素数としては、6~30が好ましく、6~20がより好ましく、6~15がさらに好ましい。
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.
直鎖脂肪族ジオール化合物として、具体的には、エチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,7-ヘプタンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-ドデカンジオール、1,18-オクタデカンジオール等が挙げられる。中でも、1,3-プロパンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール、1,10-デカンジオールが好ましい。
Specific examples of the linear aliphatic diol compound 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. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable.
分岐鎖脂肪族ジオール化合物として、具体的には、1,3-ブチレングリコール、2-メチル-1,3-プロパンジオール、ネオペンチルグリコール、3-メチル-1,5-ペンタンジオール、2-n-ブチル-2-エチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2,4-ジエチル-1,5-ペンタンジオール、1,2-ヘキサングリコール、1,2-オクチルグリコール、2-エチル-1,3-ヘキサンジオール、2-エチル-1,6-ヘキサンジオール、2,2,4-トリメチル-1,6-ヘキサンジオール、2,3-ジイソブチル-1,3-プロパンジオール、2,2-ジイソアミル-1,3-プロパンジオール、2-メチル-2-プロピル-1,3-プロパンジオール等が挙げられる。中でも、3-メチル-1,5-ペンタンジオール、2-n-ブチル-2-エチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2,4-ジエチル-1,5-ペンタンジオールが好ましい。
Specific examples of the branched aliphatic diol compound 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-propanediol. Among them, 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.
脂環式ジオール化合物としては、イソソルビド等、上記したカーボネート単位(A)を誘導することのできる脂環式ジオール化合物以外の脂環式ジオール化合物を挙げることができる。脂環式ジオール化合物として、具体的には、1,2-シクロヘキサンジオール、1,3-シクロヘキサンジオール、1,4-シクロヘキサンジオール、2-メチル-1,4-シクロヘキサンジオール等のシクロヘキサンジオール類;1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール等のシクロヘキサンジメタノール類;2,3-ノルボルナンジメタノール、2,5-ノルボルナンジメタノール等のノルボルナンジメタノール類;トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール、1,3-アダマンタンジオール、2,2-アダマンタンジオール、1,5-デカリンジメタノール、2,3-デカリンジメタノール、2,2,4,4-テトラメチル-1,3-シクロブタンジオール及び3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン等が挙げられる。これらのうち、1,4-シクロヘキサンジメタノール、トリシクロデカンジメタノール、3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンが好ましい。
Examples of the alicyclic diol compound 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, 2,2-adamantanediol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,2,4,4 -Tetramethyl-1 3-cyclobutanediol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-spiro [5.5] undecane. Of these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred.
カーボネート単位(B)を構成するこれらの脂肪族ジオール化合物及び脂環式ジオール化合物は、1種を単独で使用してもよく、2種以上を併用してもよい。また、本発明で使用されるジオール成分は、本発明の効果を損なわない範囲で、脂肪族ジオール化合物及び/又は脂環式ジオール化合物と、芳香族ジオール化合物とを併用してもよい。芳香族ジオール化合物としては、1,3-ビス[2-(4-ヒドロキシフェニル)-2-プロピル]ベンゼン(ビスフェノールM)、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサン、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルフィド、2,2’-ビス(4-ヒドロキシフェニル)プロパン(ビスフェノールA)、2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン(ビスフェノールC)、2,2-ビス(4-ヒドロキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン(ビスフェノールAF)、及び1,1-ビス(4-ヒドロキシフェニル)デカン等が挙げられる。
These aliphatic diol compounds and alicyclic diol compounds constituting the carbonate unit (B) may be used alone or in combination of two or more. Moreover, 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.
本発明で使用されるポリカーボネート(a)は、カーボネート単位(A)を含み、さらにカーボネート単位(B)を含むことが好ましい。それらカーボネート単位(A)とカーボネート単位(B)とのモル比(A)/(B)は15/85~95/5が好ましい。モル比(A)/(B)が15/85~95/5の範囲では、耐熱性が高くさらに成形性も良好となる。モル比(A)/(B)は、より好ましくは30/70~90/10、さらに好ましくは40/60~90/10、特に好ましくは50/50~90/10、最も好ましくは60/40~90/10である。なお、モル比(A)/(B)が15/85より小さい場合は、耐熱性が低くなり易く、他方モル比(A)/(B)が95/5より大きい場合は、溶融粘度が高くなり、成形性が悪化し易くなり、それに伴い、耐衝撃性が悪化し易くなる。各繰り返し単位のモル比は、例えば、高分解能フーリエ変換核磁気共鳴装置(FT-NMR)(型式:JNM-AL400、日本電子社製)、又はフーリエ変換核磁気共鳴装置(FT-NMR)(型式:JNM-ECX400、日本電子社製)を用いて、ポリカーボネート(a)について1H-NMRにて測定して算出することができる。
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. When the molar ratio (A) / (B) is in the range of 15/85 to 95/5, the heat resistance is high and the moldability is also good. 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. In addition, when the molar ratio (A) / (B) is smaller than 15/85, the heat resistance tends to be low, and when the molar ratio (A) / (B) is larger than 95/5, the melt viscosity is high. As a result, the moldability tends to deteriorate, and the impact resistance tends to deteriorate accordingly. 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.
本発明で使用されるポリカーボネート(a)は、カーボネート単位(A)とカーボネート単位(B)との合計の含有量が全カーボネート単位中70モル%以上であることが好ましく、80モル%以上であることがより好ましく、90モル%以上であることがさらに好ましく、95モル%以上であることが特に好ましく、98モル%以上であることが最も好ましい。安全性を考慮して、本発明の歯科用樹脂組成物がビスフェノール骨格を有するカーボネートを含まない実施態様においては、ポリカーボネート(a)におけるカーボネート単位(A)とカーボネート単位(B)との合計の含有量が100モル%であってもよい。
In the polycarbonate (a) used in the present invention, 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. In consideration of safety, in an embodiment in which the dental resin composition of the present invention does not contain a carbonate having a bisphenol skeleton, the total content of the carbonate unit (A) and the carbonate unit (B) in the polycarbonate (a) The amount may be 100 mol%.
本発明で使用されるポリカーボネート(a)の歯科用樹脂組成物中の含有量は、40重量%以上であることが好ましく、50重量%以上であることがより好ましく、60重量%以上であることがさらに好ましい。また、ポリカーボネート(a)の歯科用樹脂組成物中の含有量は、99重量%以下であることが好ましく、95重量%以下であることがより好ましく、90重量%以下であることがさらに好ましく、80重量%以下であることが特に好ましく、70重量%以下であることが最も好ましい。ポリカーボネート(a)の歯科用樹脂組成物中の含有量が、40~99重量%である場合、透明性及び靭性を損なうことなく、強度を向上させることができる。
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. When 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.
本発明で使用されるポリカーボネート(a)は、通常のポリカーボネート樹脂を製造するそれ自体公知の反応手段、例えばジオール成分に、カーボネート前駆物質(炭酸ジエステル等)を反応(エステル交換反応)させる方法により製造される。次にこれらの製造方法について簡単に説明する。
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.
カーボネート前駆物質として炭酸ジエステルを用いるエステル交換反応は、不活性ガス雰囲気下で所定割合のジオール成分を炭酸ジエステルと加熱しながら撹拌して、生成するアルコール又はフェノール類を留出させる方法により行われる。反応温度は生成するアルコール又はフェノール類の沸点等により異なるが、通常120~300℃の範囲である。反応はその初期から減圧にして生成するアルコール又はフェノール類を留出させながら反応を完結させるのが好ましい。また、必要に応じて末端停止剤、酸化防止剤等を加えてもよい。
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.
前記エステル交換反応に使用される炭酸ジエステルとしては、置換されていてもよい炭素数6~12のアリール基、置換されていてもよい炭素数7~13のアラルキル基等のエステルが挙げられる。具体的には、ジフェニルカーボネート、ジトリルカーボネート、ビス(クロロフェニル)カーボネート及びm-クレジルカーボネート等が挙げられる。中でもジフェニルカーボネートが特に好ましい。炭酸ジエステルの使用量は、ジオール成分の合計1モルに対して、好ましくは0.97~1.10モル、より好ましくは1.00~1.06モルである。
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.
また溶融重合法においては重合速度を速めるために、重合触媒を用いることができる。かかる重合触媒としては、例えば、アルカリ金属化合物、アルカリ土類金属化合物、塩基性ホウ素化合物、塩基性リン化合物、含窒素化合物、金属化合物等が挙げられる。
In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of 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.
このような重合触媒として使用できる化合物としては、アルカリ金属若しくはアルカリ土類金属の、有機酸塩、無機塩、酸化物、水酸化物、水素化物、アルコキシド、4級アンモニウムヒドロキシド等が好ましく用いられる。これらの化合物は1種を単独で使用してもよく、2種以上を併用してもよい。
As a compound that can be used as such a polymerization catalyst, 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.
アルカリ金属化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化リチウム、炭酸水素ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸セシウム、酢酸リチウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸セシウム、ステアリン酸リチウム、水素化ホウ素ナトリウム、安息香酸ナトリウム、安息香酸カリウム、安息香酸セシウム、安息香酸リチウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸水素二リチウム、フェニルリン酸二ナトリウム、ビスフェノールAの二ナトリウム塩、二カリウム塩、二セシウム塩、二リチウム塩、フェノールのナトリウム塩、カリウム塩、セシウム塩、リチウム塩等が挙げられる。
Examples of the alkali metal compound 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. Lithium, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate , Dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, dipotassium salt, cesium salt, dilithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt, etc. It is.
アルカリ土類金属化合物としては、例えば、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、炭酸水素カルシウム、炭酸水素バリウム、炭酸水素マグネシウム、炭酸水素ストロンチウム、二酢酸マグネシウム、二酢酸カルシウム、二酢酸ストロンチウム、二酢酸バリウム等が挙げられる。
Examples of the alkaline earth metal compound 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.
塩基性ホウ素化合物としては、例えば、テトラメチルホウ素、テトラエチルホウ素、テトラプロピルホウ素、テトラブチルホウ素、トリメチルエチルホウ素、トリメチルベンジルホウ素、トリメチルフェニルホウ素、トリエチルメチルホウ素、トリエチルベンジルホウ素、トリエチルフェニルホウ素、トリブチルベンジルホウ素、トリブチルフェニルホウ素、テトラフェニルホウ素、ベンジルトリフェニルホウ素、メチルトリフェニルホウ素、ブチルトリフェニルホウ素等のアルカリ金属塩又はアルカリ土類金属塩(ナトリウム塩、カリウム塩、リチウム塩、カルシウム塩、バリウム塩、マグネシウム塩、又はストロンチウム塩)等が挙げられる。
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 (sodium salt, potassium salt, lithium salt, calcium salt, barium salt) such as boron, tributylphenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, butyl triphenyl boron , Magnesium salt, or strontium salt).
塩基性リン化合物としては、例えば、トリエチルホスフィン、トリ-n-プロピルホスフィン、トリイソプロピルホスフィン、トリ-n-ブチルホスフィン、トリフェニルホスフィン、トリブチルホスフィン、又は四級ホスホニウム塩等が挙げられる。
Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
含窒素化合物としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド等のアルキル基又はアリール基等を有する4級アンモニウムヒドロキシド類が挙げられる。また、含窒素化合物としては、例えば、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミン等の3級アミン類;2-メチルイミダゾール、2-フェニルイミダゾール、ベンゾイミダゾール等のイミダゾール類が挙げられる。さらに、含窒素化合物としては、例えば、アンモニア、テトラメチルアンモニウムボロハイドライド、テトラブチルアンモニウムボロハイドライド、テトラブチルアンモニウムテトラフェニルボレート、テトラフェニルアンモニウムテトラフェニルボレート等の塩基又は塩基性塩等が挙げられる。
Examples of the nitrogen-containing compound 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. Examples of nitrogen-containing compounds include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Furthermore, 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.
金属化合物としては、例えば、亜鉛アルミニウム化合物、ゲルマニウム化合物、有機スズ化合物、アンチモン化合物、マンガン化合物、チタン化合物、ジルコニウム化合物等が挙げられる。
Examples of the metal compound 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.
これらの重合触媒の使用量は、ジオール成分1モルに対して、好ましくは1×10-9~1×10-2当量の範囲であり、より好ましくは1×10-8~1×10-5当量の範囲であり、さらに好ましくは1×10-7~1×10-3当量の範囲である。
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.
また、反応後期(ポリカーボネートのガラス転移温度(100℃~150℃程度)を超えた付近(Tg+10℃程度)の温度の段階)に触媒失活剤を添加することもできる。触媒失活剤としては、公知の触媒失活剤が有効に使用されるが、この中でもスルホン酸のアンモニウム塩、スルホン酸のホスホニウム塩、スルホン酸エステルが好ましい。さらに、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩等のドデシルベンゼンスルホン酸の塩類;p-トルエンスルホン酸テトラブチルアンモニウム塩等のp-トルエンスルホン酸の塩類が好ましい。
In addition, 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.)). As the catalyst deactivator, known catalyst deactivators are effectively used. Among them, sulfonic acid ammonium salts, sulfonic acid phosphonium salts, and sulfonic acid esters are preferable. Further, 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.
また、スルホン酸エステルとしては、例えば、ベンゼンスルホン酸メチル、ベンゼンスルホン酸エチル、ベンゼンスルホン酸ブチル、ベンゼンスルホン酸オクチル、ベンゼンスルホン酸フェニル、p-トルエンスルホン酸メチル、p-トルエンスルホン酸エチル、p-トルエンスルホン酸ブチル、p-トルエンスルホン酸オクチル、p-トルエンスルホン酸フェニル等が好ましく用いられる。これらの触媒失活剤の中でも、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩が最も好ましく使用される。
Examples of the sulfonate ester 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. Among these catalyst deactivators, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.
これらの触媒失活剤の使用量は、アルカリ金属化合物及びアルカリ土類金属化合物より選ばれた少なくとも1種の重合触媒を用いた場合、その重合触媒1モル当たり0.5~50モルの割合が好ましく、0.5~10モルの割合がより好ましく、0.8~5モルの割合がさらに好ましい。
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.
繊維状フィラー(b)
本発明の歯科用樹脂組成物には、強度及び弾性率を向上させるために、長さ0.5~10mm及びアスペクト比100~10000の繊維状フィラー(b)が配合される。繊維状フィラー(b)として、例えば、無機繊維状フィラー(b1)、有機繊維状フィラー(b2)等が挙げられる。 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. Examples of the fibrous filler (b) include inorganic fibrous filler (b1) and organic fibrous filler (b2).
本発明の歯科用樹脂組成物には、強度及び弾性率を向上させるために、長さ0.5~10mm及びアスペクト比100~10000の繊維状フィラー(b)が配合される。繊維状フィラー(b)として、例えば、無機繊維状フィラー(b1)、有機繊維状フィラー(b2)等が挙げられる。 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. Examples of the fibrous filler (b) include inorganic fibrous filler (b1) and organic fibrous filler (b2).
無機繊維状フィラー(b1)の材料としては、例えば、シリカ;石英繊維、ガラス繊維(チョップドストランド)、グラスウール等が挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。
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.
有機繊維状フィラー(b2)の材料としては、例えば、セルロース、キチン、キトサン、ポリエーテルエーテルケトン、ポリエーテルケトンケトン、ポリイミド、ポリアミド、ナイロン、ポリエステル、ポリアリレート、ポリカーボネート、ポリフェニレンエーテル、ポリオキシメチレン、ポリエチレン等が挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。これらの中でも、強度の観点から、セルロース、ポリエーテルエーテルケトン、ポリエーテルケトンケトン、ポリイミド、ポリアミドが好ましい。
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.
無機繊維状フィラー(b1)は、ポリカーボネート(a)との混和性を調整するため、必要に応じて公知の表面処理材で予め表面処理してから用いてもよい。表面処理材としては、例えば、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール等のアルコール類;トリエチルアミン等のアルカノールアミン;オルガノポリシロキサン等の有機シリコーン系化合物;ステアリン酸等の高級脂肪酸(炭素数12以上24以下);ステアリン酸カルシウム、ステアリン酸マグネシウム等の脂肪酸金属塩(炭素数12以上24以下);ポリエチレンワックス、流動パラフィン等の炭化水素系滑剤;リジン、アルギニン等の塩基性アミノ酸;ポリグリセリン及びその誘導体;シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等のカップリング剤等が挙げられる。これらは1種を単独で又は2種以上を併用して用いることができる。例えば、表面処理材は、アルコール類、アルカノールアミン、有機シリコーン系化合物、高級脂肪酸、脂肪酸金属塩、炭化水素系滑剤、塩基性アミノ酸、ポリグリセリン及びその誘導体、及びカップリング剤からなる群から選ばれる1種以上が挙げられる。
In order to adjust the miscibility with the polycarbonate (a), the inorganic fibrous filler (b1) may be used after being surface-treated with a known surface treatment material as necessary. Examples of 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 A silane coupling agent, a titanate coupling agent, a coupling agent such as an aluminum coupling agent, and the like. These can be used alone or in combination of two or more. For example, 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.
繊維状フィラー(b)の長さ(繊維長)は0.5~10mmである。ポリカーボネート(a)に分散した場合の透明性及び模様を生じない点、成形体に異方性を生じない点から、この長さは7.5mm以下が好ましく、5.0mm以下がより好ましい。また、前記長さは十分な補強効果を発現させる点から、1.0mm以上が好ましく、1.5mm以上がより好ましい。さらに、繊維状フィラー(b)のアスペクト比は100~10000であり、205~7500であることが好ましく、250~5000であることがより好ましい。ここでいうアスペクト比とは、繊維の長さ(μm)を繊維径(μm)で除した値である。
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 (μm) by the fiber diameter (μm).
なお、本明細書において、繊維状フィラーのアスペクト比は、光学顕微鏡又は電子顕微鏡観察により求めることができる。具体的には、繊維径0.10μm以上の繊維径測定には光学顕微鏡が、繊維径0.10μm未満の繊維の繊維径測定には電子顕微鏡観察が簡便である。
In the present specification, the aspect ratio of the fibrous filler can be determined by observation with an optical microscope or an electron microscope. Specifically, an optical microscope is simple for measuring a fiber diameter of a fiber diameter of 0.10 μm or more, and an electron microscope observation is simple for measuring a fiber diameter of a fiber having a fiber diameter of less than 0.10 μm.
繊維状フィラー(b)が無機繊維状フィラー(b1)の場合、長さは1.0~7.5mmが好ましく、1.5~5.0mmがより好ましい。また、無機繊維状フィラー(b1)のアスペクト比は、205~7500であることが好ましく、210~5000であることがより好ましく、210~3000であることがさらに好ましく、215~2000であることが特に好ましい。さらに、無機繊維状フィラー(b1)の場合、繊維径は0.10~20.0μmが好ましく、1.0~18.0μmがより好ましく、5.0~18.0μmがさらに好ましい。また、10.0μm以上であってもよい。
When the fibrous filler (b) is an inorganic fibrous filler (b1), 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. Further, in the case of the inorganic fibrous filler (b1), the fiber diameter is preferably 0.10 to 20.0 μm, more preferably 1.0 to 18.0 μm, and further preferably 5.0 to 18.0 μm. Moreover, 10.0 micrometers or more may be sufficient.
繊維状フィラー(b)が有機繊維状フィラー(b2)の場合、長さは1.0~7.5mmが好ましく、1.5~5.0mmがより好ましい。また、有機繊維状フィラー(b2)のアスペクト比は、1000~10000であることが好ましく、2000~10000であることがより好ましく、3000~9800であることがさらに好ましく、3500~9500であることが特に好ましい。さらに、有機繊維状フィラー(b2)の場合、繊維径は0.05~3.0μmが好ましく、0.10~2.0μmがより好ましい。
When the fibrous filler (b) is an organic fibrous filler (b2), 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. Further, in the case of the organic fibrous filler (b2), the fiber diameter is preferably 0.05 to 3.0 μm, more preferably 0.10 to 2.0 μm.
繊維状フィラー(b)の配合量は特に限定されないが、加工性及び歯科用樹脂組成物の強度の観点から、歯科用樹脂組成物中、1重量%以上であることが好ましく、5重量%以上であることがより好ましく、10重量%以上であることがさらに好ましく、20重量%以上であることが特に好ましく、30重量%以上であることが最も好ましい。また、繊維状フィラー(b)の配合量は、加工性、靭性が良好に保たれる点から、60重量%以下であることが好ましく、50重量%以下であることがより好ましく、40重量%以下であることがさらに好ましい。繊維状フィラー(b)の含有量が1重量%以上であると得られる歯科用樹脂組成物の強度が良好に保たれ、60重量%以下であると得られる歯科用樹脂組成物の加工性、靭性が良好に保たれる。
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. In addition, 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.
繊維状フィラー(b)としては、市販品を使用することができる。このような市販品としては、例えば、CSチョップドストランド(日東紡績社製)、セルロースナノファイバー((株)スギノマシン製)、アラミド繊維(メタ系アラミド繊維、パラ系アラミド繊維;東レ・デュポン社製)等が挙げられる。
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.
本発明の歯科用樹脂組成物には、本発明の目的を損なわない範囲で、機械的性能等の調整を目的として、繊維状フィラー(b)以外のフィラーを配合してもよい。繊維状フィラー(b)以外のフィラーとしては、例えば、板状フィラー、球状フィラー、破砕状フィラー等が挙げられる。これらの板状フィラー、球状フィラー及び破砕状フィラーは、有機フィラー及び/又は無機フィラー、あるいは有機無機複合フィラーであってもよい。これらは、繊維状フィラー(b)との合計量が本発明の歯科用樹脂組成物中、60重量%を超えないことが好ましく、45重量%を超えないことがより好ましく、40重量%を超えないことがさらに好ましい。
In the dental resin composition of the present invention, 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. Examples of 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.
また、本発明の歯科用樹脂組成物には、性能を低下させない範囲内で、公知の添加剤を配合することができる。かかる添加剤としては、例えば、酸化防止剤、着色剤(顔料、染料、繊維等)、紫外線吸収剤、有機溶媒、増粘剤等が挙げられる。本発明において、例えば、着色剤を含む樹脂組成物を使用して、透明感のある義歯床を得ることができる。これらの添加剤の配合量は、特に限定されないが、10重量%未満であってもよく、5.0重量%未満であってもよく、1.0重量%未満であってもよく、0.3重量%未満であってもよい。
In addition, the dental resin composition of the present invention can be blended with known additives within a range that does not deteriorate the performance. Examples of such additives include antioxidants, colorants (pigments, dyes, fibers, etc.), ultraviolet absorbers, organic solvents, thickeners, and the like. In the present invention, for example, 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.
本発明の歯科用樹脂組成物の製造方法に特に制限はなく、本発明の歯科用樹脂組成物は、前記ポリカーボネート(a)と前記繊維状フィラー(b)とを混合することにより製造することができる。本発明は、歯科用樹脂組成物の製造方法であって、上記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と繊維状フィラー(b)とを混合する工程を含み、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である製造方法を包含する。当該製造方法によって、上記した歯科用樹脂組成物を製造することができる。また、前記混合工程において、前記ポリカーボネート(a)と前記繊維状フィラー(b)を用いる限り、本発明の製造方法によって製造される歯科用樹脂組成物は上記した歯科用樹脂組成物の構成を満たしていなくてもよい。前記ポリカーボネート(a)と前記繊維状フィラー(b)とを混合する具体的な方法に特に制限はないが、例えば、ポリカーボネート(a)の良溶媒中でポリカーボネート(a)と共に、前記フィラー(繊維状フィラー(b)及び必要により繊維状フィラー(b)以外のフィラー)、必要により添加剤等の構成成分を混合し、次いで溶媒を除去する溶液ブレンド法;ポリカーボネート(a)と前記構成成分(繊維状フィラー(b)及び必要により繊維状フィラー(b)以外のフィラー、さらに必要により添加剤等)を二軸押出機等で溶融混練する方法等、公知の混合方法が使用可能である。このうち、前記ポリカーボネート(a)と前記繊維状フィラー(b)とを溶融混練する工程を含む方法が好ましい。最も好ましい方法は二軸押出機による溶融混練である。溶融混練時の温度は、例えば、130~350℃程度であってもよい。
There is no restriction | limiting in particular in the manufacturing method of the dental resin composition of this invention, 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. Moreover, in the said mixing process, as long as the said polycarbonate (a) and the said fibrous filler (b) are used, the dental resin composition manufactured by the manufacturing method of this invention satisfy | fills the structure of the above-mentioned dental resin composition. It does not have to be. Although there is no restriction | limiting in particular in the specific method of mixing the said polycarbonate (a) and the said fibrous filler (b), For example, the said filler (fibrous) with a polycarbonate (a) in the good solvent of a polycarbonate (a) Solution blending method in which constituents such as filler (b) and, if necessary, fillers other than fibrous filler (b), and additives as necessary are mixed, and then the solvent is removed; polycarbonate (a) and the constituents (fibrous) 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. with a twin screw extruder or the like can be used. Among these, 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.
本発明の歯科用樹脂組成物の成形体(すなわち、歯科用成形体)の用途としては、例えば、義歯床、矯正用ブラケット、人工歯等が挙げられる。義歯床は一般にクリア又は歯肉色に着色され、総義歯の義歯床、部分義歯の義歯床等があり、人工歯を支持するとともに、口腔内への装着部としての機能を果たす。更に詳しく言えば、針金(クラスプ)又は金属を基本的に使用しない有床義歯(ノンクラスプデンチャー)の義歯床、針金クラスプの存在する有床部分義歯の義歯床、さらには上記総義歯の義歯床を含む。人工歯は、義歯床と一体化されて義歯を構成するもの、口腔に直接的に植歯されるもの等がある。
Examples of uses of the molded body of the dental resin composition of the present invention (that is, a dental molded body) 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.
本発明の歯科用樹脂組成物の成形方法に特に制限はないが、例えば、ペレットから射出成形により義歯床やブラケット等の成形体を得る方法、又は、ペレットから射出成形にて一度ディスク状に成形した後、CAD/CAMシステムを用いて、切削加工する方法、あるいは、3Dプリントシステムを使用してペレットからストランド状に押し出し、積層成形する方法等、公知の成形方法が使用可能である。最も好ましい方法は射出成形、CAD/CAMシステムによる切削加工である。
The molding method of the dental resin composition of the present invention is not particularly limited. For example, 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. Thereafter, 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.
本発明は、本発明の効果を奏する限り、本発明の技術的範囲内において、上記の構成を種々組み合わせた態様を含む。
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.
次に、実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではなく、多くの変形が本発明の技術的思想内で当分野において通常の知識を有する者により可能である。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge.
[ポリマー組成比]
フーリエ変換核磁気共鳴装置(FT-NMR)(型式:JNM-ECX400、日本電子社製、測定温度=25℃)を用いて1H-NMRにて、各繰り返し単位を測定し、ポリマー組成比(モル比)を算出した。 [Polymer composition ratio]
Each repeating unit was measured by 1 H-NMR using a Fourier transform nuclear magnetic resonance apparatus (FT-NMR) (model: JNM-ECX400, manufactured by JEOL Ltd., measurement temperature = 25 ° C.), and the polymer composition ratio ( Molar ratio) was calculated.
フーリエ変換核磁気共鳴装置(FT-NMR)(型式:JNM-ECX400、日本電子社製、測定温度=25℃)を用いて1H-NMRにて、各繰り返し単位を測定し、ポリマー組成比(モル比)を算出した。 [Polymer composition ratio]
Each repeating unit was measured by 1 H-NMR using a Fourier transform nuclear magnetic resonance apparatus (FT-NMR) (model: JNM-ECX400, manufactured by JEOL Ltd., measurement temperature = 25 ° C.), and the polymer composition ratio ( Molar ratio) was calculated.
[合成例1]
ポリカーボネート(a)-1
イソソルビド(以下、ISSと略す)375g、1,6-ヘキサンジオール(以下、HDと略す)101g、ジフェニルカーボネート(以下、DPCと略す)750g、及び触媒としてテトラメチルアンモニウムヒドロキシド0.8×10-2gと水酸化ナトリウム0.6×10-4gを反応槽内で混合して窒素雰囲気下で180℃に加熱し溶融させた。その後、30分かけて減圧度を13.4kPaに調整した。その後、60℃/hrの速度で240℃まで昇温を行い、10分間その温度で保持した後、1時間かけて減圧度を133Pa以下とした。合計6時間撹拌下で反応を行い、反応槽の底より窒素加圧下吐出し、水槽で冷却しながら、ペレタイザーでカットしてペレットを得た。ポリカーボネート(a)-1のISS/HD(モル比)は75/25であった。 [Synthesis Example 1]
Polycarbonate (a) -1
375 g of isosorbide (hereinafter abbreviated as ISS), 101 g of 1,6-hexanediol (hereinafter abbreviated as HD), 750 g of diphenyl carbonate (hereinafter abbreviated as DPC), and tetramethylammonium hydroxide 0.8 × 10 − as a catalyst 2 g and 0.6 × 10 −4 g of sodium hydroxide were mixed in the reaction vessel and heated to 180 ° C. in a nitrogen atmosphere to be melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr and maintained at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. 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.
ポリカーボネート(a)-1
イソソルビド(以下、ISSと略す)375g、1,6-ヘキサンジオール(以下、HDと略す)101g、ジフェニルカーボネート(以下、DPCと略す)750g、及び触媒としてテトラメチルアンモニウムヒドロキシド0.8×10-2gと水酸化ナトリウム0.6×10-4gを反応槽内で混合して窒素雰囲気下で180℃に加熱し溶融させた。その後、30分かけて減圧度を13.4kPaに調整した。その後、60℃/hrの速度で240℃まで昇温を行い、10分間その温度で保持した後、1時間かけて減圧度を133Pa以下とした。合計6時間撹拌下で反応を行い、反応槽の底より窒素加圧下吐出し、水槽で冷却しながら、ペレタイザーでカットしてペレットを得た。ポリカーボネート(a)-1のISS/HD(モル比)は75/25であった。 [Synthesis Example 1]
Polycarbonate (a) -1
375 g of isosorbide (hereinafter abbreviated as ISS), 101 g of 1,6-hexanediol (hereinafter abbreviated as HD), 750 g of diphenyl carbonate (hereinafter abbreviated as DPC), and tetramethylammonium hydroxide 0.8 × 10 − as a catalyst 2 g and 0.6 × 10 −4 g of sodium hydroxide were mixed in the reaction vessel and heated to 180 ° C. in a nitrogen atmosphere to be melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 240 ° C. at a rate of 60 ° C./hr and maintained at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. 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.
[合成例2]
ポリカーボネート(a)-2
ISS426g、2,4-ジエチル-1,5-ペンタンジオール(以下、DEPと略す)83g、DPC750gを原料として用いた以外は合成例1と全く同様の操作を行い、ポリカーボネート(a)-2を製造した。ポリカーボネート(a)-2のISS/DEP(モル比)は85/15であった。 [Synthesis Example 2]
Polycarbonate (a) -2
Except for using ISS 426 g, 2,4-diethyl-1,5-pentanediol (hereinafter abbreviated as DEP) 83 g, and DPC 750 g as raw materials, the same operation as in Synthesis Example 1 was carried out to produce polycarbonate (a) -2. did. The ISS / DEP (molar ratio) of the polycarbonate (a) -2 was 85/15.
ポリカーボネート(a)-2
ISS426g、2,4-ジエチル-1,5-ペンタンジオール(以下、DEPと略す)83g、DPC750gを原料として用いた以外は合成例1と全く同様の操作を行い、ポリカーボネート(a)-2を製造した。ポリカーボネート(a)-2のISS/DEP(モル比)は85/15であった。 [Synthesis Example 2]
Polycarbonate (a) -2
Except for using ISS 426 g, 2,4-diethyl-1,5-pentanediol (hereinafter abbreviated as DEP) 83 g, and DPC 750 g as raw materials, the same operation as in Synthesis Example 1 was carried out to produce polycarbonate (a) -2. did. The ISS / DEP (molar ratio) of the polycarbonate (a) -2 was 85/15.
[合成例3]
ポリカーボネート(a)-3
ISS250g、1,4-シクロヘキサンジメタノール(以下、CHDMと略す)247g、DPC750gを原料として用いた以外は合成例1と全く同様の操作を行い、ポリカーボネート(a)-3を製造した。ポリカーボネート(a)-3のISS/CHDM(モル比)は50/50であった。 [Synthesis Example 3]
Polycarbonate (a) -3
Except for using ISS 250 g, 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM) 247 g, and DPC 750 g as raw materials, the same operation as in Synthesis Example 1 was carried out to produce polycarbonate (a) -3. The ISS / CHDM (molar ratio) of the polycarbonate (a) -3 was 50/50.
ポリカーボネート(a)-3
ISS250g、1,4-シクロヘキサンジメタノール(以下、CHDMと略す)247g、DPC750gを原料として用いた以外は合成例1と全く同様の操作を行い、ポリカーボネート(a)-3を製造した。ポリカーボネート(a)-3のISS/CHDM(モル比)は50/50であった。 [Synthesis Example 3]
Polycarbonate (a) -3
Except for using ISS 250 g, 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM) 247 g, and DPC 750 g as raw materials, the same operation as in Synthesis Example 1 was carried out to produce polycarbonate (a) -3. The ISS / CHDM (molar ratio) of the polycarbonate (a) -3 was 50/50.
次に、実施例又は比較例に係る歯科用樹脂組成物に用いた各成分を、略号及び略称とともに以下に説明する。
Next, each component used in the dental resin composition according to Examples or Comparative Examples will be described below together with abbreviations and abbreviations.
[繊維状フィラー(b)]
GF1:ガラス繊維(商品名:CSチョップドストランド CS 3 PE-455S、日東紡績社製、繊維長:3.0mm、アスペクト比:230、シラン系表面処理)
GF2:ガラス繊維(商品名:CSチョップドストランド CS 3.8 J-455S、日東紡績社製、繊維長:3.8mm、アスペクト比:350、シラン系表面処理)
CNF:セルロースナノファイバー(商品名:ビンフィス(BiNFi-s)、(株)スギノマシン製、繊維長1.7mm、アスペクト比 9500)
PA:パラ系アラミド繊維(商品名:ケブラー、東レ社製、繊維長4.5mm、アスペクト比 4500) [Fibrous filler (b)]
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)
GF1:ガラス繊維(商品名:CSチョップドストランド CS 3 PE-455S、日東紡績社製、繊維長:3.0mm、アスペクト比:230、シラン系表面処理)
GF2:ガラス繊維(商品名:CSチョップドストランド CS 3.8 J-455S、日東紡績社製、繊維長:3.8mm、アスペクト比:350、シラン系表面処理)
CNF:セルロースナノファイバー(商品名:ビンフィス(BiNFi-s)、(株)スギノマシン製、繊維長1.7mm、アスペクト比 9500)
PA:パラ系アラミド繊維(商品名:ケブラー、東レ社製、繊維長4.5mm、アスペクト比 4500) [Fibrous filler (b)]
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)
[酸化防止剤]
PEP-36:ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト ADEKA製 [Antioxidant]
PEP-36: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite manufactured by ADEKA
PEP-36:ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト ADEKA製 [Antioxidant]
PEP-36: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite manufactured by ADEKA
[実施例1~9及び比較例1~7]
(1)上記の構成成分を、下記表1及び2に示す割合(重量部)でそれぞれ予備混合した後、一括して二軸押出機[テクノベル(株)製 KZW15-45MG 軸径φ15mm L/D45]に供給して温度240~300℃、回転数300rpmで溶融混練し、ストランド状に押し出してストランドカッターでカットすることにより、歯科用樹脂組成物のペレットを製造した。 [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 φ15 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.
(1)上記の構成成分を、下記表1及び2に示す割合(重量部)でそれぞれ予備混合した後、一括して二軸押出機[テクノベル(株)製 KZW15-45MG 軸径φ15mm L/D45]に供給して温度240~300℃、回転数300rpmで溶融混練し、ストランド状に押し出してストランドカッターでカットすることにより、歯科用樹脂組成物のペレットを製造した。 [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 φ15 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.
(2)上記(1)で得られた歯科用樹脂組成物のペレットを用いて、射出成形機(東芝機械(株)製「IS-55EPN」、型締圧55×103kg)を使用して、溶融温度260~300℃、金型温度100℃の条件下にて射出成形して、厚さ18mm×直径10cmの円盤状のディスクを製造した。この成形品(ディスク)について、各物性を以下に記載した方法で測定した。
(2) Using the dental resin composition pellets obtained in (1) above, an injection molding machine (“IS-55EPN” manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 55 × 10 3 kg) was used. Then, injection molding was carried out under the conditions of a melting temperature of 260 to 300 ° C. and a mold temperature of 100 ° C. to produce a disk-shaped disk having a thickness of 18 mm and a diameter of 10 cm. The physical properties of this molded product (disk) were measured by the methods described below.
<曲げ強さ及び曲げ弾性率評価>
実施例及び比較例で得られた各ディスクから、厚さ3.3mm×幅10.0mm×長さ64mmの試験片を切り出した。得られた試験片について、義歯床用アクリル系レジンJIS T 6501:2012に準拠して曲げ強さ試験及び曲げ弾性率試験を行って評価した。すなわち、万能試験機(島津製作所社製、オートグラフAG-100kNI)を用いて、クロスヘッドスピード5mm/minで曲げ試験を実施した。成形体の曲げ強さとしては、150MPa以上が好ましく、170MPa以上がより好ましく、175MPa以上がさらに好ましい。成形体の曲げ弾性率としては、3500MPa以上が好ましく、3900MPa以上がより好ましく、4000MPa以上がさらに好ましい。 <Evaluation of bending strength and flexural modulus>
A test piece having a thickness of 3.3 mm, a width of 10.0 mm, and a length of 64 mm was cut out from each of the disks obtained in Examples and Comparative Examples. About the obtained test piece, based on acrylic resin JIS T 6501: 2012 for denture bases, the bending strength test and the bending elastic modulus test were done and evaluated. That is, using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-100kNI), a bending test was performed at a crosshead speed of 5 mm / min. 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.
実施例及び比較例で得られた各ディスクから、厚さ3.3mm×幅10.0mm×長さ64mmの試験片を切り出した。得られた試験片について、義歯床用アクリル系レジンJIS T 6501:2012に準拠して曲げ強さ試験及び曲げ弾性率試験を行って評価した。すなわち、万能試験機(島津製作所社製、オートグラフAG-100kNI)を用いて、クロスヘッドスピード5mm/minで曲げ試験を実施した。成形体の曲げ強さとしては、150MPa以上が好ましく、170MPa以上がより好ましく、175MPa以上がさらに好ましい。成形体の曲げ弾性率としては、3500MPa以上が好ましく、3900MPa以上がより好ましく、4000MPa以上がさらに好ましい。 <Evaluation of bending strength and flexural modulus>
A test piece having a thickness of 3.3 mm, a width of 10.0 mm, and a length of 64 mm was cut out from each of the disks obtained in Examples and Comparative Examples. About the obtained test piece, based on acrylic resin JIS T 6501: 2012 for denture bases, the bending strength test and the bending elastic modulus test were done and evaluated. That is, using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-100kNI), a bending test was performed at a crosshead speed of 5 mm / min. 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.
<靭性評価(全破壊仕事)>
実施例及び比較例で得られた各ディスクから、厚さ8.0mm、幅3.0mm、長さ39mm、ノッチ深さ3.0mmの試験片を切り出した。得られた試験片について、JIS T 6501:2012に準拠して破壊靭性試験を行って、全破壊仕事を評価した。全破壊仕事が4.0kJ/m2を超える値であれば成形体は靭性に優れ、5.0kJ/m2以上が好ましい。 <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.
実施例及び比較例で得られた各ディスクから、厚さ8.0mm、幅3.0mm、長さ39mm、ノッチ深さ3.0mmの試験片を切り出した。得られた試験片について、JIS T 6501:2012に準拠して破壊靭性試験を行って、全破壊仕事を評価した。全破壊仕事が4.0kJ/m2を超える値であれば成形体は靭性に優れ、5.0kJ/m2以上が好ましい。 <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.
<表面性状評価(平滑性及び縞模様)>
上記の破壊靭性試験の試験片から縦横8.0mm×厚さ3.0mmの試験片を切り出した。得られた試験片を、#1000のシリコン・カーバイド紙(日本研紙社製)を用いて研磨し、続いて、#3000のラッピングフィルム(3M製)を用いて、さらに研磨して、平滑面とした。当該平滑面を、3Dレーザー顕微鏡(キーエンス製)を用いて、縦横1.0mmの範囲について表面粗さ(JIS B 0601:2013の最大山高さRp)を測定した。試験片の5箇所の測定値の平均値を表面性状(平滑性)の指標とした。口腔内で使用した時に、チクチク感等の違和感を感じる恐れが小さい点から、Rpが150μm以下が好ましく、100μm以下がより好ましい。さらに、前記のようにして、破壊靭性試験の試験片から切り出した試験片について、縞模様の有無を目視にて観察した。 <Surface property evaluation (smoothness and striped pattern)>
A test piece having a length and width of 8.0 mm and a thickness of 3.0 mm was cut out from the test piece of the fracture toughness test. The obtained test piece was polished using # 1000 silicon carbide paper (manufactured by Nihon Kenshi), and then further polished using a # 3000 wrapping film (manufactured by 3M) to obtain a smooth surface. It was. Using a 3D laser microscope (manufactured by Keyence), the smooth surface was measured for surface roughness (maximum peak height Rp of JIS B 0601: 2013) in a range of 1.0 mm in length and width. 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 μm or less, and more preferably 100 μm 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.
上記の破壊靭性試験の試験片から縦横8.0mm×厚さ3.0mmの試験片を切り出した。得られた試験片を、#1000のシリコン・カーバイド紙(日本研紙社製)を用いて研磨し、続いて、#3000のラッピングフィルム(3M製)を用いて、さらに研磨して、平滑面とした。当該平滑面を、3Dレーザー顕微鏡(キーエンス製)を用いて、縦横1.0mmの範囲について表面粗さ(JIS B 0601:2013の最大山高さRp)を測定した。試験片の5箇所の測定値の平均値を表面性状(平滑性)の指標とした。口腔内で使用した時に、チクチク感等の違和感を感じる恐れが小さい点から、Rpが150μm以下が好ましく、100μm以下がより好ましい。さらに、前記のようにして、破壊靭性試験の試験片から切り出した試験片について、縞模様の有無を目視にて観察した。 <Surface property evaluation (smoothness and striped pattern)>
A test piece having a length and width of 8.0 mm and a thickness of 3.0 mm was cut out from the test piece of the fracture toughness test. The obtained test piece was polished using # 1000 silicon carbide paper (manufactured by Nihon Kenshi), and then further polished using a # 3000 wrapping film (manufactured by 3M) to obtain a smooth surface. It was. Using a 3D laser microscope (manufactured by Keyence), the smooth surface was measured for surface roughness (maximum peak height Rp of JIS B 0601: 2013) in a range of 1.0 mm in length and width. 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 μm or less, and more preferably 100 μm 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.
上記結果から、本発明の歯科用樹脂組成物は、得られる成形体の曲げ強さと曲げ弾性率と靭性が高く、縞模様もなく外観にも優れ、高い平滑性を有し、使用感にも優れることが確認できた。これに対し、繊維状フィラーを配合していない比較例1の組成物、長さの短い繊維状フィラーを配合した比較例2及び3の組成物は、得られる成形体の曲げ強さと曲げ弾性率が低く、比較例2及び3の組成物では靱性も低かった。一方、繊維長が長い繊維状フィラーを配合した比較例4の組成物は、研磨面が粗く縞模様も見られ、表面性状が悪かった。さらに、ビスフェノール系ポリカーボネートを使用した比較例5及び6の組成物は、得られる成形体の曲げ強さが低く、また研磨面も実施例の場合に比べて粗かった。ビスフェノール系ポリカーボネートと繊維長が短い繊維状フィラーとを併用した比較例7の組成物は、得られる成形体の曲げ強さと曲げ弾性率が低く、靱性も低かった。ここで例えば、実施例1と比較例2との比較、及び、比較例5と比較例7との比較などから、ポリカーボネート(a)と繊維状フィラー(b)とが併用されることにより、曲げ強さや表面性状が相乗的に向上することが分かる。
From the above results, 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. On the other hand, 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. On the other hand, the 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 composition of Comparative Example 7 in which a bisphenol-based polycarbonate and a fibrous filler having a short fiber length were used in combination had low bending strength and flexural modulus of the resulting molded article, and low toughness. Here, for example, from the comparison between Example 1 and Comparative Example 2, and the comparison between Comparative Example 5 and Comparative Example 7, etc., 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.
本発明の歯科用樹脂組成物は、成形体の曲げ強さと曲げ弾性率と靭性が高く、成形体の表面性状が良好であり、特に義歯床に有用である。
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.
Claims (11)
- 下記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と、繊維状フィラー(b)とを含有し、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である、歯科用樹脂組成物。
- さらに、前記ポリカーボネート(a)が、脂肪族ジオール化合物及び脂環式ジオール化合物からなる群より選ばれる少なくとも1種の化合物から誘導されるカーボネート単位(B)を含む、請求項1に記載の歯科用樹脂組成物。 Furthermore, the said polycarbonate (a) contains the carbonate unit (B) derived from the at least 1 sort (s) of compound chosen from the group which consists of an aliphatic diol compound and an alicyclic diol compound, The dental use of Claim 1 Resin composition.
- 前記ポリカーボネート(a)において、カーボネート単位(A)とカーボネート単位(B)とのモル比((A)/(B))が、15/85~95/5である、請求項2に記載の歯科用樹脂組成物。 The dental composition according to claim 2, wherein in the polycarbonate (a), the molar ratio ((A) / (B)) of the carbonate unit (A) to the carbonate unit (B) is 15/85 to 95/5. Resin composition.
- 前記ポリカーボネート(a)の含有量が、40~99重量%である、請求項1~3のいずれかに記載の歯科用樹脂組成物。 The dental resin composition according to any one of claims 1 to 3, wherein the content of the polycarbonate (a) is 40 to 99% by weight.
- 前記繊維状フィラー(b)が無機繊維状フィラー(b1)であり、前記無機繊維状フィラー(b1)のアスペクト比が205~7500である、請求項1~4のいずれかに記載の歯科用樹脂組成物。 The dental resin according to any one of claims 1 to 4, wherein the fibrous filler (b) is an inorganic fibrous filler (b1), and the aspect ratio of the inorganic fibrous filler (b1) is 205 to 7500. Composition.
- 前記繊維状フィラー(b)が有機繊維状フィラー(b2)であり、前記有機繊維状フィラー(b2)のアスペクト比が1000~10000である、請求項1~4のいずれかに記載の歯科用樹脂組成物。 The dental resin according to any one of claims 1 to 4, wherein the fibrous filler (b) is an organic fibrous filler (b2), and the organic fibrous filler (b2) has an aspect ratio of 1000 to 10,000. Composition.
- 歯科用樹脂組成物の製造方法であって、下記式(A)で表されるカーボネート単位(A)を15モル%以上98モル%以下含むポリカーボネート(a)と繊維状フィラー(b)とを混合する工程を含み、前記繊維状フィラー(b)の長さが0.5~10mmであり、かつアスペクト比が100~10000である、製造方法。
- 前記混合する工程が溶融混練する工程を含む、請求項7に記載の製造方法。 The manufacturing method according to claim 7, wherein the mixing step includes a melt-kneading step.
- 請求項7又は8の製造方法によって製造される歯科用樹脂組成物。 A dental resin composition produced by the production method according to claim 7 or 8.
- 請求項1~6及び9のいずれかに記載の歯科用樹脂組成物からなる歯科用成形体。 A dental molded body comprising the dental resin composition according to any one of claims 1 to 6 and 9.
- 義歯床である請求項10に記載の歯科用成形体。 The dental molded body according to claim 10, which is a denture base.
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JP2020193299A (en) * | 2019-05-30 | 2020-12-03 | 株式会社トクヤマデンタル | Hydrophilic surface-treating agent |
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