WO2020137927A1 - Thermoplastic resin and method for producing same, and optical lens comprising said thermoplastic resin - Google Patents

Thermoplastic resin and method for producing same, and optical lens comprising said thermoplastic resin Download PDF

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WO2020137927A1
WO2020137927A1 PCT/JP2019/050234 JP2019050234W WO2020137927A1 WO 2020137927 A1 WO2020137927 A1 WO 2020137927A1 JP 2019050234 W JP2019050234 W JP 2019050234W WO 2020137927 A1 WO2020137927 A1 WO 2020137927A1
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Prior art keywords
carbon atoms
ppb
thermoplastic resin
atom
dicarboxylic acid
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PCT/JP2019/050234
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French (fr)
Japanese (ja)
Inventor
篤志 茂木
健太朗 石原
克吏 西森
慎也 池田
加藤　宣之
近藤　光輝
健輔 大島
正大 神田
章子 鈴木
龍展 緒方
三豪 末松
隆実 森下
平川　学
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三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to JP2020563228A priority Critical patent/JP7548015B2/en
Priority to KR1020217013301A priority patent/KR20210108943A/en
Priority to CN201980085972.6A priority patent/CN113260883A/en
Publication of WO2020137927A1 publication Critical patent/WO2020137927A1/en
Priority to JP2024058426A priority patent/JP2024079821A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the present invention relates to a thermoplastic resin, a method for producing the same, and an optical lens including the thermoplastic resin. More specifically, it relates to a thermoplastic resin having a high refractive index, a high heat resistance and a low YI value, and an optical lens including the same.
  • Optical glass or optical resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras.
  • Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has the problems of high material cost, poor moldability, and low productivity.
  • optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resins, etc. are used as high refractive index materials for camera lenses.
  • resins having a high refractive index has been required due to the lighter, thinner, shorter and smaller products.
  • a lens element having the same refractive index can be realized by a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, and It is possible to reduce the polarization sensitivity and reduce the lens thickness to reduce the weight.
  • An object of the present invention is to provide a thermoplastic resin having a high refractive index, a high heat resistance, and a low YI value, a method for producing the same, and an optical lens including the thermoplastic resin.
  • thermoplastic resin using a dicarboxylic acid containing a specific metal in a specific amount, and have reached the present invention. did.
  • thermoplastic resin by reacting at least a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid, It is a production method in which the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S.
  • a and b each independently represent an integer of 0 to 5.
  • the metal is 1 to 100 ppb for Li, 2 to 500 ppb for Na, 1 to 1000 ppb for Mg, 5 to 500 ppb for Al, 20 to 3000 ppb for K, 5 to 1000 ppb for Ca, 1 to 100 ppb for Ti, and 1 to 100 ppb for Cr.
  • the composition containing a dicarboxylic acid represented by the above formula (1) and a metal derived from the dicarboxylic acid is reacted with a diol compound represented by the following formula (2).
  • R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S.
  • thermoplastic resin is polyester or polyester carbonate.
  • thermoplastic resin comprising a constitutional unit represented by the following formula (3) and a metal derived from a dicarboxylic acid constituting the constitutional unit:
  • the metal is a thermoplastic resin containing Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
  • R 5 and R 6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S.
  • thermoplastic resin according to ⁇ 7> wherein the thermoplastic resin has a YI value of 7 to 40.
  • thermoplastic resin of the present invention has a high refractive index, a high heat resistance and a low YI value, and can exert an excellent effect particularly when used in an optical lens.
  • FIG. 1 is the NMR measurement result of the polyester resin obtained in Example 1.
  • the method for producing a thermoplastic resin of the present invention is a method for producing a thermoplastic resin by reacting at least a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid.
  • the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S.
  • R 1 and R 2 each independently represent a hydrogen atom, a phenyl group, a naphthyl group or a substituent selected from the group consisting of the following.
  • a and b each independently represent an integer of 0 to 5, and preferably each independently represent 0 or 1.
  • 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl and the compounds represented by the following structural formulas are preferable, and 2,2′-bis (Hydroxycarbonylmethoxy)-1,1′-binaphthyl is particularly preferred.
  • the 1,1′-binaphthyl skeleton improves the heat resistance and refractive index of the thermoplastic resin, and has a conformation orthogonal to the bond axis connecting the two naphthalene rings. Therefore, there is an effect of reducing birefringence.
  • the binaphthyl skeleton may be any of R-form, S-form, and racemic form, and preferably the racemic form.
  • the racemate which does not require optical resolution, has a cost advantage.
  • the metal derived from the dicarboxylic acid represented by the formula (1) means a metal component mixed as an impurity when the dicarboxylic acid represented by the formula (1) is produced.
  • metals include Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, Sn, V, Mn, Co, Cu, Ge, Sr, Zr, Mo, Ag, Cd.
  • the metal derived from the dicarboxylic acid represented by the formula (1) has a total content of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn of 10,000 ppb or less.
  • thermoplastic resin by reacting a dicarboxylic acid containing Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less. It was surprisingly found that a thermoplastic resin having a high refractive index, a high heat resistance and a low YI value can be obtained.
  • the metal derived from the dicarboxylic acid represented by the formula (1) is Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 54 ppb. It is preferable to include the above amount.
  • the metal derived from the dicarboxylic acid represented by the formula (1) preferably contains Fe in an amount of 20 to 3000 ppb. Also, 1 to 100 ppb for Li, 2 to 500 ppb for Na, 1 to 1000 ppb for Mg, 5 to 500 ppb for Al, 20 to 3000 ppb for K, 5 to 1000 ppb for Ca, 1 to 100 ppb for Ti, 5 to 500 ppb for Cr, It is preferable to contain Ni in an amount of 1 to 100 ppb, Zn in an amount of 2 to 100 ppb, and Sn in an amount of 1 to 100 ppb. Table 1 below shows the more preferable content of each metal component and the upper limit of the particularly preferable content.
  • the thermoplastic resin of the present invention obtained by the above-mentioned production method is a thermoplastic resin containing a structural unit represented by the following formula (3) and a metal derived from a dicarboxylic acid constituting the structural unit:
  • the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
  • R 5 , R 6 , e and f have the same meanings as R 1 , R 2 , a and b in the formula (1), respectively.
  • a specific thermoplastic resin is preferably a polyester resin or a polyester carbonate resin, and particularly preferably a polyester resin from the viewpoint of the effect of the present invention.
  • thermoplastic resin of the present invention has a high refractive index, and the refractive index at a measurement wavelength of 589 nm at 25° C. (hereinafter sometimes abbreviated as “nD”) is 1.650 to 1 It is preferably 0.720, more preferably 1.660 to 1.710, still more preferably 1.670 to 1.700.
  • nD the refractive index at a measurement wavelength of 589 nm at 25° C.
  • nD the refractive index at a measurement wavelength of 589 nm at 25° C.
  • Tg glass transition point
  • thermoplastic resin of the present invention has a low YI value, and the YI value is preferably from 7 to 40, more preferably from 9 to 38. Furthermore, the thermoplastic resin of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 50,000, more preferably 15,000 to 40,000. As a method for measuring the weight average molecular weight (Mw), the method described in Examples below can be used.
  • thermoplastic resin of the present invention is not particularly limited as long as it is obtained by reacting a composition containing a dicarboxylic acid represented by the formula (1) and a metal derived from the dicarboxylic acid. Any diol compound may be used as the raw material. In the present invention, it is preferable to react a composition containing a dicarboxylic acid represented by the above formula (1) and a metal derived from the dicarboxylic acid with a diol compound represented by the following formula (2).
  • R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. It represents an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a selected heterocyclic atom. ..
  • R 3 and R 4 each independently represent a hydrogen atom, a phenyl group, a naphthyl group or a substituent selected from the group consisting of the following.
  • c and d each independently represent an integer of 0 to 5, and preferably each independently represent 0 or 1.
  • the thermoplastic resin in the present invention has a constitutional unit represented by the above formula (3), preferably a constitutional unit derived from a diol compound represented by the above formula (2). It may contain components.
  • the copolymerization component include dicarboxylic acid components other than those represented by the above formula (1), diol components other than those represented by the above formula (2), and repeating units having a carbonate bond.
  • dicarboxylic acid component as a copolymerization component
  • dicarboxylic acid component examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethyldicarboxylic acid components such as ethylmalonic acid.
  • Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid and terephthalic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid , Polycyclic aromatic dicarboxylic acid components such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid, biphenyl dicarboxylic acid components such as 2,2′-biphenyldicarboxylic acid, 1,4-cyclodicarboxylic acid, 2,6-decalindicarboxylic acid, etc. Alicyclic dicarboxylic acid component of.
  • a monocyclic aromatic dicarboxylic acid component a polycyclic aromatic dicarboxylic acid component, and a biphenyl dicarboxylic acid component are preferable because they can easily increase the heat resistance and the refractive index.
  • diol component as a copolymerization component examples include aliphatic diol components such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and nonanediol, and tricyclo[5.2].
  • ethylene glycol and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl are preferable because they can easily suppress the deterioration of heat resistance and refractive index while improving the moldability.
  • repeating unit having a carbonate bond as a copolymerization component examples include those in which the diol component exemplified in the formula (2) and the diol component exemplified as the above-mentioned copolymerization component are carbonate-bonded.
  • thermoplastic resin of the present invention is obtained by subjecting the dicarboxylic acid and diol compound represented by the above formula (1) to an esterification reaction or a transesterification reaction, and subjecting the obtained reaction product to a polycondensation reaction to obtain a desired high molecular weight compound. It may be a molecular weight substance.
  • the diol component and the dicarboxylic acid component or its diester in the presence of an inert gas, and react under reduced pressure usually at 120 to 350°C, preferably at 150 to 300°C. ..
  • the degree of pressure reduction is changed stepwise, and finally water or alcohol produced at 0.13 kPa or less is distilled out of the system, and the reaction time is usually about 1 to 10 hours.
  • antimony compounds, titanium compounds, germanium compounds, tin compounds or aluminum compounds are preferable.
  • antimony compounds, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates are preferable.
  • these compounds can be used in combination of 2 or more types.
  • tin, titanium and germanium compounds are preferable from the viewpoint of melt stability and hue of the thermoplastic resin.
  • the transesterification catalyst one known per se can be adopted, and for example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or a lead element can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Of these, compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, and alcoholates are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and small amount of polymer-insoluble foreign matter. Further, manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more kinds.
  • the thermoplastic resin of the present invention may contain a copolymerization component other than the constitutional unit represented by the formula (3).
  • a copolymerization component other than the constitutional unit represented by the formula (3).
  • dicarboxylic acid chloride or phosgene may be reacted in addition to the diol component and the dicarboxylic acid component, or the polyester carbonate resin can be produced by reacting the diol, dicarboxylic acid and biaryl carbonate. ..
  • biaryl carbonate examples include carbonic acid diesters such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.
  • the content of the dicarboxylic acid chloride, phosgene, or biaryl carbonate component is preferably less than 42 mol%, more preferably less than 30 mol%, and further preferably less than 20 mol% with respect to 100 mol% of the dicarboxylic acid component.
  • thermoplastic resin of the present invention if necessary, additives such as a heat stabilizer, an antioxidant, a release agent, a plasticizer, a filler, and an ultraviolet absorber are appropriately added to obtain a thermoplastic resin composition. Can be used.
  • the release agent it is preferable that 90% by weight or more thereof is composed of an ester of alcohol and fatty acid.
  • the ester of alcohol and fatty acid include esters of monohydric alcohol and fatty acid and/or partial or total ester of polyhydric alcohol and fatty acid.
  • the ester of monohydric alcohol and fatty acid is preferably an ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms.
  • the partial or total ester of polyhydric alcohol and fatty acid is preferably partial ester or total ester of polyhydric alcohol having 1 to 25 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms.
  • ester of monohydric alcohol and saturated fatty acid examples include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, with stearyl stearate being preferred.
  • partial or whole ester of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetraglyceride.
  • esters or parts of dipentaerythritol such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate.
  • esters include esters.
  • stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
  • the amount of the ester in the release agent is preferably 90% by weight or more, more preferably 95% by weight or more, based on 100% by weight of the release agent.
  • the release agent to be added to the thermoplastic resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, based on 100 parts by weight of the thermoplastic resin. A range of 0.02 to 0.5 parts by weight is more preferable.
  • the heat stabilizer examples include phosphorus-based heat stabilizers, sulfur-based heat stabilizers and hindered phenol-based heat stabilizers.
  • phosphorus-based heat stabilizer tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite is preferably used.
  • the content of the phosphorus-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • hindered phenol heat stabilizers octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is particularly preferably used.
  • the content of the hindered phenolic heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.
  • UV absorber at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic iminoester UV absorbers and cyanoacrylate UV absorbers. Is preferred.
  • benzotriazole type ultraviolet absorbers more preferable are 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethyl Butyl)-6-(2H-benzotriazol-2-yl)phenol].
  • benzophenone-based ultraviolet absorber examples include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.
  • triazine-based ultraviolet absorber examples include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis( 2.4-Dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol and the like can be mentioned.
  • cyclic imino ester-based ultraviolet absorber 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) is particularly preferable.
  • the blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the blending amount is within the above range, a thermoplastic resin molded article can be prepared according to the application. It is possible to impart sufficient weather resistance.
  • the thermoplastic resin of the present invention is suitable for optical members, particularly optical lenses.
  • the optical lens containing the thermoplastic resin of the present invention is manufactured by injection molding, it is preferable to mold under the conditions of a cylinder temperature of 260 to 350° C. and a mold temperature of 90 to 170° C. More preferably, molding is performed under the conditions of a cylinder temperature of 270 to 320° C. and a mold temperature of 100 to 160° C. If the cylinder temperature is higher than 350°C, the thermoplastic resin is decomposed and colored, and if it is lower than 260°C, the melt viscosity is high and molding tends to be difficult.
  • the mold temperature is higher than 170° C., it tends to be difficult to take out the molded piece made of the thermoplastic resin from the mold.
  • the mold temperature is lower than 90°C, the resin may harden too quickly in the mold at the time of molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Is likely to be difficult.
  • the optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary. Since it is possible to reduce the spherical aberration to substantially zero with a single aspherical lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the molding cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
  • the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens that is thin, small, and has a complicated shape.
  • the thickness of the central portion is preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further preferably 0.1 to 2.0 mm.
  • the diameter is preferably 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, still more preferably 3.0 to 10.0 mm.
  • the meniscus lens has a convex shape on one side and a concave shape on one side.
  • the optical lens of the present invention is molded by any method such as mold molding, cutting, polishing, laser processing, electric discharge machining, and etching. Among these, die molding is more preferable from the viewpoint of manufacturing cost.
  • Mw ⁇ (Wi ⁇ Mi) ⁇ (Wi)
  • i the i-th division point when the molecular weight M is divided
  • Wi the i-th weight
  • Mi the i-th molecular weight.
  • the molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve.
  • HLC-8320GPC manufactured by Tosoh Corporation was used as a GPC device, one TSKguardcolumn SuperMPHZ-M was used as a guard column, and three TSKgel SuperMultiporeHZ-M were connected in series as an analytical column. Other conditions are as follows.
  • nD, ⁇ d ⁇ Method of measuring refractive index (nD, ⁇ d)> The obtained resin was press-molded into a disc having a diameter of 40 mm and a thickness of 3 mm (molding condition: 200° C., 100 kgf/cm 2 , 2 minutes), cut out at a right angle, and measured at a wavelength of 589 nm at 25° C. by KPR-200 manufactured by Kalnew. The refractive index was measured.
  • BINOL-DC 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl
  • BINOL-DC 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl
  • DP-BHBNA 2,2′-bis(2-hydroxyethoxy)-6,6′diphenyl-1,1′-binaphthalene
  • EG ethylene glycol
  • EG ethylene glycol
  • Example 2 A polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl of different lots was used. Table 2 shows the physical properties of the obtained polyester resin.
  • BINOL-DC-A 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl used in Example 1 was designated as BINOL-DC-A, and 2,2′-bis used in Example 2 was used.
  • BINOL-DC-B 2,2′-bis used in Example 2 was used.
  • Example 3 Further, a polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl of different lot was used. Table 2 shows the physical properties of the obtained polyester resin. In Table 2, 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl used in Example 3 was designated as BINOL-DC-C.
  • Example 4 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl (BINOL-DC-A) 50.29 g (0.12 mol) used in Example 1, represented by the following structural formula 9,9 '-Bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) 164.41 g (0.37 mol), diphenyl carbonate 55.95 g (0.26 mol) and 0.015 g of tetrabutoxy titanium as a catalyst Then, the mixture was placed in a reaction kettle equipped with a distillation device, heated to 180° C. under a nitrogen atmosphere at atmospheric pressure, and stirred for 30 minutes.
  • BPEF BPEF
  • Example 2 A polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl containing the amount of metal shown in Table 2 below was used. Table 2 shows the physical properties of the obtained polyester resin.
  • thermoplastic resin of the present invention Since the thermoplastic resin of the present invention has a high refractive index, high heat resistance and low YI value, it is an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a substrate, an optical filter. It can be used as an optical member such as a hard coat film, and is particularly useful as a lens for a camera such as a smartphone, a DSC, and a vehicle. By using the thermoplastic resin of the present invention, it is possible to reduce the thickness of the lens unit used for telephoto and the like.

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Abstract

According to the present invention, it is possible to provide a method for producing a thermoplastic resin by reacting a composition comprising at least a dicarboxylic acid represented by formula (1) and a metal component derived from the dicarboxylic acid, wherein the metal component contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in the total amount of 10000 ppb or less. (In formula (1), R1 and R2 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms each of which may contain a hetero ring atom selected from O, N and S; and a and b independently represent an integer of 0 to 5.)

Description

熱可塑性樹脂及びその製造方法並びに該熱可塑性樹脂を含む光学レンズThermoplastic resin, method for producing the same, and optical lens containing the thermoplastic resin
  本発明は、熱可塑性樹脂及びその製造方法並びに該熱可塑性樹脂を含む光学レンズに関する。更に詳しくは、高屈折率、高耐熱性及び低いＹＩ値を有する熱可塑性樹脂およびそれを含む光学レンズに関する。 The present invention relates to a thermoplastic resin, a method for producing the same, and an optical lens including the thermoplastic resin. More specifically, it relates to a thermoplastic resin having a high refractive index, a high heat resistance and a low YI value, and an optical lens including the same.
  カメラ、フィルム一体型カメラ、ビデオカメラ等の各種カメラの光学系に使用される光学レンズの材料として、光学ガラスあるいは光学用樹脂が使用されている。光学ガラスは、耐熱性、透明性、寸法安定性、耐薬品性等に優れるが、材料コストが高く、成形加工性が悪く、生産性が低いという問題点を有している。 Optical glass or optical resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has the problems of high material cost, poor moldability, and low productivity.
  一方、光学用樹脂からなる光学レンズは、射出成形により大量生産が可能であるという利点を有しており、カメラレンズ用高屈折率材料としてポリカーボネート、ポリエステルカーボネート、ポリエステル樹脂等が使用されている。しかしながら、近年、製品の軽薄短小化により、高い屈折率の樹脂の開発が求められている。一般に光学材料の屈折率が高いと、同一の屈折率を有するレンズエレメントを、より曲率の小さい面で実現できるため、この面で発生する収差量を小さくでき、レンズの枚数を減らしたり、レンズの偏光感度を低減したり、レンズ厚みを薄くして軽量化することが可能になる。 On the other hand, optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resins, etc. are used as high refractive index materials for camera lenses. However, in recent years, development of resins having a high refractive index has been required due to the lighter, thinner, shorter and smaller products. Generally, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized by a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, and It is possible to reduce the polarization sensitivity and reduce the lens thickness to reduce the weight.
  光学用樹脂を光学レンズとして用いる場合、屈折率やアッベ数以外にも、耐熱性、透明性、低吸水性、耐薬品性、低複屈折、耐湿熱性が求められる。特に近年、高屈折率および高耐熱性を有する光学レンズが求められており、様々な樹脂の開発が行われているが（特許文献１～４）、更に優れた高屈折率および高耐熱性を有する光学レンズが求められているのが現状である。 When using an optical resin as an optical lens, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and moist heat resistance are required in addition to the refractive index and Abbe number. Particularly in recent years, there has been a demand for an optical lens having a high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 4), but further excellent high refractive index and high heat resistance are required. At present, there is a demand for an optical lens having the same.
特開２０１８－２８９３号公報Japanese Patent Laid-Open No. 2018-2893 特開２０１８－２８９４号公報Japanese Patent Laid-Open No. 2018-2894 特開２０１８－２８９５号公報JP, 2008-2895, A 特開２０１８－５９０７４号公報JP, 2018-59074, A
  本発明は、高屈折率及び高耐熱性、更には低いＹＩ値を有する熱可塑性樹脂及びその製造方法並びに該熱可塑性樹脂を含む光学レンズを提供することを課題とする。 An object of the present invention is to provide a thermoplastic resin having a high refractive index, a high heat resistance, and a low YI value, a method for producing the same, and an optical lens including the thermoplastic resin.
  本発明者らは鋭意研究を重ねた結果、特定の金属を特定の量で含有するジカルボン酸を用いて熱可塑性樹脂を製造することにより、上記課題を解決することができることを見出し本発明に到達した。 As a result of intensive studies conducted by the present inventors, they have found that the above problems can be solved by producing a thermoplastic resin using a dicarboxylic acid containing a specific metal in a specific amount, and have reached the present invention. did.
  すなわち、本発明は、以下の通りである。
＜１＞　少なくとも、下記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物を反応させて熱可塑性樹脂を製造する方法であって、
　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含む、製造方法である。
Figure JPOXMLDOC01-appb-C000004
 （式（１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ａおよびｂは、それぞれ独立して０～５の整数を表す。）
＜２＞　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnを合計で５４ｐｐｂ以上の量で含む、上記＜１＞に記載の製造方法である。
＜３＞　前記金属が、Feを２０～３０００ｐｐｂの量で含む、上記＜１＞または＜２＞に記載の製造方法である。
＜４＞　前記金属が、Liを１～１００ｐｐｂ、Naを２～５００ｐｐｂ、Mgを１～１０００ｐｐｂ、Alを５～５００ｐｐｂ、Kを２０～３０００ｐｐｂ、Caを５～１０００ｐｐｂ、Tiを１～１００ｐｐｂ、Crを５～５００ｐｐｂ、Niを１～１００ｐｐｂ、Znを２～１００ｐｐｂ、Sn を１～１００ｐｐｂの量で含む、上記＜１＞～＜３＞のいずれかに記載の製造方法である。
＜５＞　前記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物に、下記式（２）で表されるジオール化合物を反応させる、上記＜１＞～＜４＞のいずれかに記載の製造方法である。
Figure JPOXMLDOC01-appb-C000005
 （式（２）中、Ｒ３およびＲ４は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ｃおよびｄは、それぞれ独立して０～５の整数を表す。）
＜６＞　前記熱可塑性樹脂が、ポリエステルまたはポリエステルカーボネートである、上記＜１＞～＜５＞のいずれかに記載の製造方法である。
＜７＞　下記式（３）で表される構成単位と、該構成単位を構成するジカルボン酸に由来する金属とを含む熱可塑性樹脂であって、
　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含む、熱可塑性樹脂である。
Figure JPOXMLDOC01-appb-C000006
 （式（３）中、Ｒ５およびＲ６は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ｅおよびｆは、それぞれ独立して０～５の整数を表す。）
＜８＞　前記熱可塑性樹脂が７～４０のＹＩ値を有する、上記＜７＞に記載の熱可塑性樹脂である。
＜９＞　上記＜７＞または＜８＞に記載の熱可塑性樹脂を含む、光学レンズである。 That is, the present invention is as follows.
<1> A method for producing a thermoplastic resin by reacting at least a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid,
It is a production method in which the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
Figure JPOXMLDOC01-appb-C000004
 (In the formula (1), R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and a and b each independently represent an integer of 0 to 5.)
<2> The production method according to <1>, wherein the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 54 ppb or more. is there.
<3> The production method according to <1> or <2>, wherein the metal contains Fe in an amount of 20 to 3000 ppb.
<4> The metal is 1 to 100 ppb for Li, 2 to 500 ppb for Na, 1 to 1000 ppb for Mg, 5 to 500 ppb for Al, 20 to 3000 ppb for K, 5 to 1000 ppb for Ca, 1 to 100 ppb for Ti, and 1 to 100 ppb for Cr. Is 5 to 500 ppb, Ni is 1 to 100 ppb, Zn is 2 to 100 ppb, and Sn is 1 to 100 ppb in the amount of 1 to 100 ppb.
<5> The composition containing a dicarboxylic acid represented by the above formula (1) and a metal derived from the dicarboxylic acid is reacted with a diol compound represented by the following formula (2). 4> The production method according to any one of 4>.
Figure JPOXMLDOC01-appb-C000005
 (In the formula (2), R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and c and d each independently represent an integer of 0 to 5.)
<6> The production method according to any one of <1> to <5>, wherein the thermoplastic resin is polyester or polyester carbonate.
<7> A thermoplastic resin comprising a constitutional unit represented by the following formula (3) and a metal derived from a dicarboxylic acid constituting the constitutional unit:
The metal is a thermoplastic resin containing Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
Figure JPOXMLDOC01-appb-C000006
 (In the formula (3), R 5 and R 6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and e and f each independently represent an integer of 0 to 5.)
<8> The thermoplastic resin according to <7>, wherein the thermoplastic resin has a YI value of 7 to 40.
<9> An optical lens including the thermoplastic resin according to <7> or <8>.
  本発明の熱可塑性樹脂は、高屈折率、高耐熱性及び低ＹＩ値を有し、特に光学レンズに用いた場合に優れた効果を発揮することができる。 The thermoplastic resin of the present invention has a high refractive index, a high heat resistance and a low YI value, and can exert an excellent effect particularly when used in an optical lens.
図１は、実施例１で得られたポリエステル樹脂のＮＭＲ測定結果である。FIG. 1 is the NMR measurement result of the polyester resin obtained in Example 1.
  本発明をさらに詳しく説明する。
  本発明の熱可塑性樹脂の製造方法は、少なくとも、下記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物を反応させて熱可塑性樹脂を製造する方法であって、前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含むものである。
Figure JPOXMLDOC01-appb-C000007
 　式（１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。好ましくは、Ｒ１およびＲ２は、それぞれ独立して、水素原子、フェニル基、ナフチル基または下記からなる群より選択される置換基を表す。
Figure JPOXMLDOC01-appb-C000008
 　ａおよびｂは、それぞれ独立して０～５の整数を表し、好ましくはそれぞれ独立して０または１を表す。
　式（１）で表される化合物のなかでも、２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチル、及び下記構造式で表される化合物が好ましく、２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルが特に好ましい。
Figure JPOXMLDOC01-appb-C000009
 The present invention will be described in more detail.
The method for producing a thermoplastic resin of the present invention is a method for producing a thermoplastic resin by reacting at least a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid. The metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
Figure JPOXMLDOC01-appb-C000007
 In formula (1), R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. It represents an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a selected heterocyclic atom. .. Preferably, R 1 and R 2 each independently represent a hydrogen atom, a phenyl group, a naphthyl group or a substituent selected from the group consisting of the following.
Figure JPOXMLDOC01-appb-C000008
 a and b each independently represent an integer of 0 to 5, and preferably each independently represent 0 or 1.
Among the compounds represented by the formula (1), 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl and the compounds represented by the following structural formulas are preferable, and 2,2′-bis (Hydroxycarbonylmethoxy)-1,1′-binaphthyl is particularly preferred.
Figure JPOXMLDOC01-appb-C000009
  前記式（１）において、１，１’－ビナフチル骨格は、熱可塑性樹脂の耐熱性と屈折率を向上させるとともに、二つのナフタレン環を結ぶ結合軸で直交するような立体配座になっているため、複屈折を低減させる効果がある。
  また、ビナフチル骨格は、Ｒ体、Ｓ体、ラセミ体のいずれでもよく、好ましくは、ラセミ体がよい。光学分割する必要のないラセミ体はコストメリットがある。 In the above formula (1), the 1,1′-binaphthyl skeleton improves the heat resistance and refractive index of the thermoplastic resin, and has a conformation orthogonal to the bond axis connecting the two naphthalene rings. Therefore, there is an effect of reducing birefringence.
The binaphthyl skeleton may be any of R-form, S-form, and racemic form, and preferably the racemic form. The racemate, which does not require optical resolution, has a cost advantage.
　本発明において、前記式（１）で表されるジカルボン酸に由来する金属とは、前記式（１）で表されるジカルボン酸を製造する際に不純物として混入した金属成分を意味する。そのような金属としては、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn、Sn、V、Mn、Co、Cu、Ge、Sr、Zr、Mo、Ag、Cd、Sb、Ba、W、Pbなどが挙げられるが、これらのうち、V、Mn、Co、Cu、Ge、Sr、Zr、Mo、Ag、Cd、Sb、Ba、W及びPbについては検出限界（＜０．００５μｇ／ｇ）以下であるため、本発明では、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnの合計含有量を測定する。
　本発明では、前記式（１）で表されるジカルボン酸に由来する金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnを合計で１００００ｐｐｂ以下の量で含むことを特徴とし、より好ましくは５８７０ｐｐｂ以下の量で含み、特に好ましくは３７３８ｐｐｂ以下の量で含む。本発明者らは、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnを合計で１００００ｐｐｂ以下の量で含むジカルボン酸を反応させて熱可塑性樹脂を製造することによって、驚くべきことに高屈折率、高耐熱性及び低いＹＩ値を有する熱可塑性樹脂が得られることを見出した。
　また、本発明では、前記式（１）で表されるジカルボン酸に由来する金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnを合計で５４ｐｐｂ以上の量で含むことが好ましい。 In the present invention, the metal derived from the dicarboxylic acid represented by the formula (1) means a metal component mixed as an impurity when the dicarboxylic acid represented by the formula (1) is produced. Such metals include Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, Sn, V, Mn, Co, Cu, Ge, Sr, Zr, Mo, Ag, Cd. , Sb, Ba, W, Pb and the like, among them, V, Mn, Co, Cu, Ge, Sr, Zr, Mo, Ag, Cd, Sb, Ba, W and Pb detection limit ( Since it is <0.005 μg/g) or less, the total content of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn is measured in the present invention.
In the present invention, the metal derived from the dicarboxylic acid represented by the formula (1) has a total content of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn of 10,000 ppb or less. It is characterized in that it is contained in an amount, more preferably in an amount of 5870 ppb or less, particularly preferably in an amount of 3738 ppb or less. The present inventors produce a thermoplastic resin by reacting a dicarboxylic acid containing Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less. It was surprisingly found that a thermoplastic resin having a high refractive index, a high heat resistance and a low YI value can be obtained.
Further, in the present invention, the metal derived from the dicarboxylic acid represented by the formula (1) is Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 54 ppb. It is preferable to include the above amount.
　本発明において、前記式（１）で表されるジカルボン酸に由来する金属は、Feを２０～３０００ｐｐｂの量で含むことが好ましい。また、Liを１～１００ｐｐｂ、Naを２～５００ｐｐｂ、Mgを１～１０００ｐｐｂ、Alを５～５００ｐｐｂ、Kを２０～３０００ｐｐｂ、Caを５～１０００ｐｐｂ、Tiを１～１００ｐｐｂ、Crを５～５００ｐｐｂ、Niを１～１００ｐｐｂ、Znを２～１００ｐｐｂ、Sn を１～１００ｐｐｂの量で含むことが好ましい。以下の表１に各金属成分のより好ましい含有量及び特に好ましい含有量の上限値を示す。 In the present invention, the metal derived from the dicarboxylic acid represented by the formula (1) preferably contains Fe in an amount of 20 to 3000 ppb. Also, 1 to 100 ppb for Li, 2 to 500 ppb for Na, 1 to 1000 ppb for Mg, 5 to 500 ppb for Al, 20 to 3000 ppb for K, 5 to 1000 ppb for Ca, 1 to 100 ppb for Ti, 5 to 500 ppb for Cr, It is preferable to contain Ni in an amount of 1 to 100 ppb, Zn in an amount of 2 to 100 ppb, and Sn in an amount of 1 to 100 ppb. Table 1 below shows the more preferable content of each metal component and the upper limit of the particularly preferable content.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　上述した製造方法によって得られる本発明の熱可塑性樹脂は、下記式（３）で表される構成単位と、該構成単位を構成するジカルボン酸に由来する金属とを含む熱可塑性樹脂であって、前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含むものである。
Figure JPOXMLDOC01-appb-C000011
 　式（３）中、Ｒ５、Ｒ６、ｅおよびｆは、それぞれ前記式（１）におけるＲ１、Ｒ２、ａおよびｂと同義である。具体的な熱可塑性樹脂としてはポリエステル樹脂またはポリエステルカーボネート樹脂であることが好ましく、特に本発明の効果の点からポリエステル樹脂であることが好ましい。 The thermoplastic resin of the present invention obtained by the above-mentioned production method is a thermoplastic resin containing a structural unit represented by the following formula (3) and a metal derived from a dicarboxylic acid constituting the structural unit: The metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
Figure JPOXMLDOC01-appb-C000011
 In the formula (3), R 5 , R 6 , e and f have the same meanings as R 1 , R 2 , a and b in the formula (1), respectively. A specific thermoplastic resin is preferably a polyester resin or a polyester carbonate resin, and particularly preferably a polyester resin from the viewpoint of the effect of the present invention.
  本発明の熱可塑性樹脂は、高屈折率であることが特徴の一つであり、２５℃で測定波長５８９ｎｍの屈折率（以下、「ｎＤ」と略すことがある）は、１．６５０～１．７２０であることが好ましく、１．６６０～１．７１０であるとさらに好ましく、１．６７０～１．７００であるとよりさらに好ましい。
　また、本発明の熱可塑性樹脂は、高耐熱性であることが特徴の一つであり、ガラス転移点（以下、「Ｔｇ」と略することがある）は、１３０～１６０℃であることが好ましく、１４０～１５５℃であることがより好ましい。
　また、本発明の熱可塑性樹脂は、低いＹＩ値を有することが特徴の一つであり、ＹＩ値は、７～４０であることが好ましく、９～３８であることがより好ましい。
　更に、本発明の熱可塑性樹脂は、重量平均分子量（Ｍｗ）が好ましくは１０，０００～５０，０００であり、より好ましくは１５，０００～４０，０００である。重量平均分子量（Ｍｗ）の測定方法としては、後述する実施例に記載された方法を用いることができる。 One feature of the thermoplastic resin of the present invention is that it has a high refractive index, and the refractive index at a measurement wavelength of 589 nm at 25° C. (hereinafter sometimes abbreviated as “nD”) is 1.650 to 1 It is preferably 0.720, more preferably 1.660 to 1.710, still more preferably 1.670 to 1.700.
One of the characteristics of the thermoplastic resin of the present invention is high heat resistance, and the glass transition point (hereinafter, may be abbreviated as “Tg”) is 130 to 160°C. It is preferably 140 to 155°C, and more preferably.
Further, one feature of the thermoplastic resin of the present invention is that it has a low YI value, and the YI value is preferably from 7 to 40, more preferably from 9 to 38.
Furthermore, the thermoplastic resin of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 50,000, more preferably 15,000 to 40,000. As a method for measuring the weight average molecular weight (Mw), the method described in Examples below can be used.
　本発明の熱可塑性樹脂は、前記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物を反応させて得られたものであれば特に制限されるものではなく、原料としていずれのジオール化合物を用いてもよい。
　本発明においては、前記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物に、下記式（２）で表されるジオール化合物を反応させることが好ましい。
Figure JPOXMLDOC01-appb-C000012
 　式（２）中、Ｒ３およびＲ４は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。好ましくは、Ｒ３およびＲ４は、それぞれ独立して、水素原子、フェニル基、ナフチル基または下記からなる群より選択される置換基を表す。
Figure JPOXMLDOC01-appb-C000013
 　ｃおよびｄは、それぞれ独立して０～５の整数を表し、好ましくはそれぞれ独立して０または１を表す。 The thermoplastic resin of the present invention is not particularly limited as long as it is obtained by reacting a composition containing a dicarboxylic acid represented by the formula (1) and a metal derived from the dicarboxylic acid. Any diol compound may be used as the raw material.
In the present invention, it is preferable to react a composition containing a dicarboxylic acid represented by the above formula (1) and a metal derived from the dicarboxylic acid with a diol compound represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000012
 In formula (2), R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. It represents an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a selected heterocyclic atom. .. Preferably, R 3 and R 4 each independently represent a hydrogen atom, a phenyl group, a naphthyl group or a substituent selected from the group consisting of the following.
Figure JPOXMLDOC01-appb-C000013
 c and d each independently represent an integer of 0 to 5, and preferably each independently represent 0 or 1.
＜その他の共重合成分＞
  本発明における熱可塑性樹脂は、前記式（３）で表される構成単位を有し、好ましくは前記式（２）で表されるジオール化合物に由来する構成単位を有するが、それとは別に共重合成分を含んでいてもよい。共重合成分としては前記式（１）で示される以外のジカルボン酸成分、前記式（２）で示される以外のジオール成分、さらにカーボネート結合を有する繰り返し単位などが例示される。 <Other copolymerization components>
The thermoplastic resin in the present invention has a constitutional unit represented by the above formula (3), preferably a constitutional unit derived from a diol compound represented by the above formula (2). It may contain components. Examples of the copolymerization component include dicarboxylic acid components other than those represented by the above formula (1), diol components other than those represented by the above formula (2), and repeating units having a carbonate bond.
  具体的な共重合成分としてのジカルボン酸成分としては、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、メチルマロン酸、エチルマロン酸等の脂肪族ジカルボン酸成分、フタル酸、イソフタル酸、テレフタル酸等の単環式芳香族ジカルボン酸成分、２，７－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、１，４－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸、アントラセンジカルボン酸、フェナントレンジカルボン酸等の多環式芳香族ジカルボン酸成分、２，２’－ビフェニルジカルボン酸等のビフェニルジカルボン酸成分、１，４－シクロジカルボン酸、２，６－デカリンジカルボン酸等の脂環族ジカルボン酸成分が挙げられる。これらは単独または二種類以上組み合わせて用いてもよい。また、これらの誘導体としては酸クロライドやエステル類を用いてもよい。これらの中でも耐熱性と屈折率をより高くしやすいことから単環式芳香族ジカルボン酸成分、多環式芳香族ジカルボン酸成分、ビフェニルジカルボン酸成分が好ましい。 Specific examples of the dicarboxylic acid component as a copolymerization component include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethyldicarboxylic acid components such as ethylmalonic acid. Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid and terephthalic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid , Polycyclic aromatic dicarboxylic acid components such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid, biphenyl dicarboxylic acid components such as 2,2′-biphenyldicarboxylic acid, 1,4-cyclodicarboxylic acid, 2,6-decalindicarboxylic acid, etc. Alicyclic dicarboxylic acid component of. You may use these individually or in combination of 2 or more types. Moreover, you may use acid chloride and ester as these derivatives. Among these, a monocyclic aromatic dicarboxylic acid component, a polycyclic aromatic dicarboxylic acid component, and a biphenyl dicarboxylic acid component are preferable because they can easily increase the heat resistance and the refractive index.
  また、具体的な共重合成分としてのジオール成分としては、エチレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール、ヘプタンジオール、オクタンジオール、ノナンジオール等の脂肪族ジオール成分、トリシクロ［５．２．１．０２，６ ］デカンジメタノール、シクロヘキサン－１，４－ジメタノール、デカリン－２，６－ジメタノール、ノルボルナンジメタノール、ペンタシクロペンタデカンジメタノール、シクロペンタン－１，３－ジメタノール、スピログリコール、イソソルビド等の脂環式ジオール成分、ヒドロキノン、レゾルシノール、２，２－ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（３－メチル－４－ヒドロキシフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、ビス（４－ヒドロキシフェニル）ジフェニルメタン、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（４－ヒドロキシフェニル）スルホン、ビス（４－（２－ヒドロキシエトキシ）フェニル）スルホン、ビス（４－ヒドロキシフェニル）スルフィド、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、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、ビフェノール、２，２’－ビス（２－ヒドロキシエトキシ）－１，１’－ビナフチル、１，１’－ビ－２－ナフトール、ジヒドロキシナフタレン、ビス（２－ヒドロキシエトキシ）ナフタレン、１０，１０－ビス（４－ヒドロキシフェニル）アントロン等の芳香族ジオール成分等が挙げられる。これらは単独または二種類以上組み合わせて用いてもよい。これらの中でも成形性を高めつつ、耐熱性や屈折率の低下を抑えやすいことからエチレングリコールや２，２’－ビス（２－ヒドロキシエトキシ）－１，１’－ビナフチルが好ましい。 Specific examples of the diol component as a copolymerization component include aliphatic diol components such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and nonanediol, and tricyclo[5.2]. 1.02,6]] Decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornanedimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiro Alicyclic diol components such as glycol and isosorbide, hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis (4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, bis(4-hydroxyphenyl)sulfone , Bis(4-(2-hydroxyethoxy)phenyl) sulfone, bis(4-hydroxyphenyl) sulfide, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl)cyclohexane, biphenol, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene, bis(2-hydroxyethoxy) ) Aromatic diol components such as naphthalene and 10,10-bis(4-hydroxyphenyl)anthrone are listed. You may use these individually or in combination of 2 or more types. Among these, ethylene glycol and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl are preferable because they can easily suppress the deterioration of heat resistance and refractive index while improving the moldability.
  また、具体的な共重合成分としてのカーボネート結合を有する繰り返し単位としては、前記式（２）で例示したジオール成分および前述の共重合成分として例示したジオール成分をカーボネート結合させたものが挙げられる。 Further, specific examples of the repeating unit having a carbonate bond as a copolymerization component include those in which the diol component exemplified in the formula (2) and the diol component exemplified as the above-mentioned copolymerization component are carbonate-bonded.
  本発明の熱可塑性樹脂は、前述の式（１）で表されるジカルボン酸およびジオール化合物をエステル化反応もしくはエステル交換反応させ、得られた反応生成物を重縮合反応させ、所望の分子量の高分子量体とすればよい。 The thermoplastic resin of the present invention is obtained by subjecting the dicarboxylic acid and diol compound represented by the above formula (1) to an esterification reaction or a transesterification reaction, and subjecting the obtained reaction product to a polycondensation reaction to obtain a desired high molecular weight compound. It may be a molecular weight substance.
  具体的には、例えば不活性ガスの存在下で、ジオール成分と、ジカルボン酸成分またはそのジエステルを混合し、減圧下、通常、１２０～３５０℃、好ましくは１５０～３００℃で反応させることが好ましい。減圧度は段階的に変化させ、最終的には０．１３ｋＰａ以下にして生成した水または、アルコール類を系外に留去させ、反応時間は通常１～１０時間程度である。 Specifically, for example, it is preferable to mix the diol component and the dicarboxylic acid component or its diester in the presence of an inert gas, and react under reduced pressure usually at 120 to 350°C, preferably at 150 to 300°C. .. The degree of pressure reduction is changed stepwise, and finally water or alcohol produced at 0.13 kPa or less is distilled out of the system, and the reaction time is usually about 1 to 10 hours.
  重合触媒としては、それ自体公知のものを採用でき、例えば、アンチモン化合物、チタン化合物、ゲルマニウム化合物、スズ化合物またはアルミニウム化合物が好ましい。このような化合物としては、例えばアンチモン、チタン、ゲルマニウム、スズ、アルミニウムの酸化物、酢酸塩、カルボン酸塩、水素化物、アルコラート、ハロゲン化物、炭酸塩、硫酸塩等を挙げることができる。また、これらの化合物は二種以上組み合わせて使用できる。この中でも、熱可塑性樹脂の溶融安定性、色相の観点からスズ、チタン、ゲルマニウム化合物が好ましい。 As the polymerization catalyst, those known per se can be adopted, and for example, antimony compounds, titanium compounds, germanium compounds, tin compounds or aluminum compounds are preferable. Examples of such compounds include antimony, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates. Moreover, these compounds can be used in combination of 2 or more types. Among these, tin, titanium and germanium compounds are preferable from the viewpoint of melt stability and hue of the thermoplastic resin.
  エステル交換触媒としては、それ自体公知のものを採用でき、例えば、マンガン、マグネシウム、チタン、亜鉛、アルミニウム、カルシウム、コバルト、ナトリウム、リチウム、または鉛元素を含む化合物などを用いることができる。具体的にはこれらの元素を含む酸化物、酢酸塩、カルボン酸塩、水素化物、アルコラート、ハロゲン化物、炭酸塩、硫酸塩等を挙げることができる。この中でも、熱可塑性樹脂の溶融安定性、色相、ポリマー不溶異物の少なさの観点からマンガン、マグネシウム、亜鉛、チタン、コバルトの酸化物、酢酸塩、アルコラート等の化合物が好ましい。さらにマンガン、マグネシウム、チタン化合物が好ましい。これらの化合物は二種以上組み合わせて使用できる。 As the transesterification catalyst, one known per se can be adopted, and for example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or a lead element can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Of these, compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, and alcoholates are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and small amount of polymer-insoluble foreign matter. Further, manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more kinds.
  なお、本発明の熱可塑性樹脂は、前述の通り、前記式（３）で表される構成単位以外の共重合成分を含有させてもよい。例えば、ポリエステルカーボネート樹脂とする場合は、ジオール成分およびジカルボン酸成分の他に、ジカルボン酸クロライドやホスゲンを反応させてもよく、またはジオール、ジカルボン酸およびビアリールカーボネートを反応させることにより製造することができる。 Note that, as described above, the thermoplastic resin of the present invention may contain a copolymerization component other than the constitutional unit represented by the formula (3). For example, when the polyester carbonate resin is used, dicarboxylic acid chloride or phosgene may be reacted in addition to the diol component and the dicarboxylic acid component, or the polyester carbonate resin can be produced by reacting the diol, dicarboxylic acid and biaryl carbonate. ..
  ビアリールカーボネートの具体例としては、ジフェニルカーボネート、ジ－ｐ－トリルカーボネート、フェニル－ｐ－トリルカーボネート、ジ－ｐ－クロロフェニルカーボネート、ジナフチルカーボネート等の炭酸ジエステルが挙げられる。なかでもジフェニルカーボネートが好ましい。 Specific examples of the biaryl carbonate include carbonic acid diesters such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.
  該ジカルボン酸クロライドやホスゲン、またはビアリールカーボネート成分の含有量は、ジカルボン酸成分１００ｍоｌ％に対し、好ましくは４２ｍоｌ％未満、より好ましくは３０ｍоｌ％未満、さらに好ましくは２０ｍоｌ％未満である。 The content of the dicarboxylic acid chloride, phosgene, or biaryl carbonate component is preferably less than 42 mol%, more preferably less than 30 mol%, and further preferably less than 20 mol% with respect to 100 mol% of the dicarboxylic acid component.
＜添加剤＞
  本発明の熱可塑性樹脂には、必要に応じて、熱安定剤、酸化防止剤、離型剤、可塑剤、充填剤、紫外線吸収剤などの添加剤を適宜添加して熱可塑性樹脂組成物として用いることができる。 <Additive>
To the thermoplastic resin of the present invention, if necessary, additives such as a heat stabilizer, an antioxidant, a release agent, a plasticizer, a filler, and an ultraviolet absorber are appropriately added to obtain a thermoplastic resin composition. Can be used.
  離型剤としては、その９０重量％以上がアルコールと脂肪酸のエステルからなるものが好ましい。アルコールと脂肪酸のエステルとしては、具体的には一価アルコールと脂肪酸のエステルおよび／または多価アルコールと脂肪酸との部分エステルあるいは全エステルが挙げられる。前記一価アルコールと脂肪酸のエステルとは、炭素原子数１～２０の一価アルコールと炭素原子数１０～３０の飽和脂肪酸とのエステルが好ましい。また、多価アルコールと脂肪酸との部分エステルあるいは全エステルとは、炭素原子数１～２５の多価アルコールと炭素原子数１０～３０の飽和脂肪酸との部分エステルまたは全エステルが好ましい。具体的に一価アルコールと飽和脂肪酸とのエステルとしては、ステアリルステアレート、パルミチルパルミテート、ブチルステアレート、メチルラウレート、イソプロピルパルミテート等があげられ、ステアリルステアレートが好ましい。 As the release agent, it is preferable that 90% by weight or more thereof is composed of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include esters of monohydric alcohol and fatty acid and/or partial or total ester of polyhydric alcohol and fatty acid. The ester of monohydric alcohol and fatty acid is preferably an ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. The partial or total ester of polyhydric alcohol and fatty acid is preferably partial ester or total ester of polyhydric alcohol having 1 to 25 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, with stearyl stearate being preferred.
  具体的に多価アルコールと飽和脂肪酸との部分エステルまたは全エステルとしては、ステアリン酸モノグリセリド、ステアリン酸ジグリセリド、ステアリン酸トリグリセリド、ステアリン酸モノソルビテート、ベヘニン酸モノグリセリド、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトラペラルゴネート、プロピレングリコールモノステアレート、ビフェニルビフェネ－ト、ソルビタンモノステアレート、２－エチルヘキシルステアレート、ジペンタエリスリトールヘキサステアレート等のジペンタエリスルトールの全エステルまたは部分エステル等が挙げられる。これらのエステルのなかでも、ステアリン酸モノグリセリド、ステアリン酸トリグリセリド、ペンタエリスリトールテトラステアレート、ステアリン酸トリグリセリドとステアリルステアレートの混合物が好ましく用いられる。 Specific examples of the partial or whole ester of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetraglyceride. All esters or parts of dipentaerythritol such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate. Examples thereof include esters. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
  離型剤中の前記エステルの量は、離型剤を１００重量％とした時、９０重量％以上が好ましく、９５重量％以上がより好ましい。
  熱可塑性樹脂組成物に配合させる離型剤としては、熱可塑性樹脂１００重量部に対して０．００５～２．０重量部の範囲が好ましく、０．０１～０．６重量部の範囲がより好ましく、０．０２～０．５重量部の範囲がさらに好ましい。 The amount of the ester in the release agent is preferably 90% by weight or more, more preferably 95% by weight or more, based on 100% by weight of the release agent.
The release agent to be added to the thermoplastic resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, based on 100 parts by weight of the thermoplastic resin. A range of 0.02 to 0.5 parts by weight is more preferable.
  熱安定剤としては、リン系熱安定剤、硫黄系熱安定剤およびヒンダードフェノール系熱安定剤が挙げられる。
  リン系熱安定剤において、好ましくはテトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４’－ビフェニレンジホスホナイトが使用される。
  熱可塑性樹脂のリン系熱安定剤の含有量としては、熱可塑性樹脂１００重量部に対して０．００１～０．２重量部が好ましい。 Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers and hindered phenol-based heat stabilizers.
In the phosphorus-based heat stabilizer, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite is preferably used.
The content of the phosphorus-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  ヒンダードフェノール系熱安定剤において、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートが特に好ましく用いられる。
  熱可塑性樹脂中のヒンダードフェノール系熱安定剤の含有量としては、熱可塑性樹脂１００重量部に対して０．００１～０．３重量部が好ましい。 Among the hindered phenol heat stabilizers, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is particularly preferably used.
The content of the hindered phenolic heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.
  紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、環状イミノエステル系紫外線吸収剤およびシアノアクリレート系からなる群より選ばれた少なくとも１種の紫外線吸収剤が好ましい。 As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic iminoester UV absorbers and cyanoacrylate UV absorbers. Is preferred.
  ベンゾトリアゾール系紫外線吸収剤において、より好ましくは、２－（２－ヒドロキシ－５－ｔｅｒｔ－オクチルフェニル）ベンゾトリアゾ－ル、２，２’－メチレンビス［４－（１，１，３，３－テトラメチルブチル）－６－（２Ｈ－ベンゾトリアゾール－２－イル）フェノール］である。ベンゾフェノン系紫外線吸収剤としては、２－ヒドロキシ－４－ｎ－ドデシルオキシベンソフェノン、２－ヒドロキシ－４－メトキシ－２’－カルボキシベンゾフェノンが挙げられる。トリアジン系紫外線吸収剤としては、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール、２－（４，６－ビス（２．４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－［（オクチル）オキシ］－フェノール等が挙げられる。環状イミノエステル系紫外線吸収剤としては、特に２，２’－ｐ－フェニレンビス（３，１－ベンゾオキサジン－４－オン）が好適である。 Among the benzotriazole type ultraviolet absorbers, more preferable are 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethyl Butyl)-6-(2H-benzotriazol-2-yl)phenol]. Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis( 2.4-Dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol and the like can be mentioned. As the cyclic imino ester-based ultraviolet absorber, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) is particularly preferable.
  紫外線吸収剤の配合量は、熱可塑性樹脂１００重量部に対して好ましくは０．０１～３．０重量部であり、かかる配合量の範囲であれば、用途に応じ、熱可塑性樹脂成形品に十分な耐候性を付与することが可能である。 The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the blending amount is within the above range, a thermoplastic resin molded article can be prepared according to the application. It is possible to impart sufficient weather resistance.
＜光学レンズ＞
  本発明の熱可塑性樹脂は、光学部材、特に光学レンズに好適である。
  本発明の熱可塑性樹脂を含む光学レンズを射出成型で製造する場合、シリンダー温度２６０～３５０℃、金型温度９０～１７０℃の条件にて成形することが好ましい。さらに好ましくは、シリンダー温度２７０～３２０℃、金型温度１００～１６０℃の条件にて成形することが好ましい。シリンダー温度が３５０℃より高い場合では、熱可塑性樹脂が分解着色し、２６０℃より低い場合では、溶融粘度が高く成形が困難になりやすい。また金型温度が１７０℃より高い場合では、熱可塑性樹脂からなる成形片が金型から取り出すことが困難になりやすい。他方、金型温度が、９０℃未満では、成型時の金型内で樹脂が早く固まり過ぎて成形片の形状が制御しにくくなったり、金型に付された賦型を十分に転写することが困難になりやすい。 <Optical lens>
The thermoplastic resin of the present invention is suitable for optical members, particularly optical lenses.
When the optical lens containing the thermoplastic resin of the present invention is manufactured by injection molding, it is preferable to mold under the conditions of a cylinder temperature of 260 to 350° C. and a mold temperature of 90 to 170° C. More preferably, molding is performed under the conditions of a cylinder temperature of 270 to 320° C. and a mold temperature of 100 to 160° C. If the cylinder temperature is higher than 350°C, the thermoplastic resin is decomposed and colored, and if it is lower than 260°C, the melt viscosity is high and molding tends to be difficult. Further, if the mold temperature is higher than 170° C., it tends to be difficult to take out the molded piece made of the thermoplastic resin from the mold. On the other hand, if the mold temperature is lower than 90°C, the resin may harden too quickly in the mold at the time of molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Is likely to be difficult.
  本発明の光学レンズは、必要に応じて非球面レンズの形を用いることが好適に実施される。非球面レンズは、１枚のレンズで球面収差を実質的にゼロとすることが可能であるため、複数の球面レンズの組み合わせで球面収差を取り除く必要が無く、軽量化および成形コストの低減化が可能になる。したがって、非球面レンズは、光学レンズの中でも特にカメラレンズとして有用である。 The optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary. Since it is possible to reduce the spherical aberration to substantially zero with a single aspherical lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the molding cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
  また、本発明の光学レンズは、成形流動性が高いため、薄肉小型で複雑な形状である光学レンズの材料として特に有用である。具体的なレンズサイズとして、中心部の厚みが０．０５～３．０ｍｍであることが好ましく、より好ましくは０．０５～２．０ｍｍ、さらに好ましくは０．１～２．０ｍｍである。また、直径が１．０ｍｍ～２０．０ｍｍであることが好ましく、より好ましくは１．０～１０．０ｍｍ、さらに好ましくは、３．０～１０．０ｍｍである。また、その形状として片面が凸、片面が凹であるメニスカスレンズであることが好ましい。 Since the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens that is thin, small, and has a complicated shape. As a specific lens size, the thickness of the central portion is preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further preferably 0.1 to 2.0 mm. The diameter is preferably 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, still more preferably 3.0 to 10.0 mm. Further, it is preferable that the meniscus lens has a convex shape on one side and a concave shape on one side.
  本発明の光学レンズは、金型成形、切削、研磨、レーザー加工、放電加工、エッチングなど任意の方法により成形される。この中でも、製造コストの面から金型成形がより好ましい。 The optical lens of the present invention is molded by any method such as mold molding, cutting, polishing, laser processing, electric discharge machining, and etching. Among these, die molding is more preferable from the viewpoint of manufacturing cost.
  以下に実施例を挙げて本発明をさらに説明するが、本発明は、これらに限定されるものではない。なお、各物性の測定は次に示す方法で行った。 The present invention will be further described below with reference to examples, but the present invention is not limited to these. In addition, the measurement of each physical property was performed by the method shown below.
＜金属分析＞
　試料の硫酸炭化を行った後、ICP-MSにより金属濃度を測定した。
　即ち、合成石英ビーカーに試料2gを秤量し、炭化時2.5ml、炭化前に0.1mlの硫酸を加えながらホットプレート上で加熱し炭化した。引き続き、石英皿でフタをし、電気炉で500℃、10時間、加熱し、炭化した。さらに、硫酸を加え加熱し乾固、硝酸を加え加熱し乾固することにより、加熱酸分解を行った。硝酸水溶液を加え50mLとし、50℃に加温し、ICP-MSによる定量分析を行った。
　ICP-MS装置：株式会社島津製作所：ＩＣＰＥ－９０００ <Metal analysis>
After sulfuric acid carbonization of the sample, the metal concentration was measured by ICP-MS.
That is, 2 g of the sample was weighed in a synthetic quartz beaker and heated on a hot plate while adding 2.5 ml of sulfuric acid at the time of carbonization and 0.1 ml of sulfuric acid before carbonization. Subsequently, the lid was covered with a quartz dish, and heated in an electric furnace at 500° C. for 10 hours to carbonize. Furthermore, sulfuric acid was added and heated to dryness, and nitric acid was added and heated to dryness to perform thermal acid decomposition. A nitric acid aqueous solution was added to make 50 mL, and the mixture was heated to 50°C and quantitatively analyzed by ICP-MS.
ICP-MS equipment: Shimadzu Corporation: ICPE-9000
＜重量平均分子量（Ｍｗ）の測定方法＞
　予め作成した標準ポリスチレンの検量線からポリスチレン換算重量平均分子量を求めた。即ち、分子量既知（分子量分布＝１）の標準ポリスチレン（東ソー株式会社製、“PStQuick MP-M”）を用いて検量線を作成し、測定した標準ポリスチレンから各ピークの溶出時間と分子量値をプロットし、３次式による近似を行い、較正曲線とした。Ｍｗは、以下の計算式より求めた。
　　Ｍｗ＝Σ（Ｗｉ×Ｍｉ）÷Σ（Ｗｉ）
　ここで、ｉは分子量Ｍを分割した際のｉ番目の分割点、Ｗｉはｉ番目の重量、Ｍｉはｉ番目の分子量を表す。また分子量Ｍとは、較正曲線の同溶出時間でのポリスチレン分子量値を表す。ＧＰＣ装置として、東ソー株式会社製、ＨＬＣ－８３２０ＧＰＣを用い、ガードカラムとして、TSKguardcolumn SuperMPHZ-Mを１本、分析カラムとしてTSKgel SuperMultiporeHZ-Mを３本直列に連結したものを用いた。その他の条件は以下の通りである。
　　溶媒：ＨＰＬＣグレードテトラヒドロフラン
　　注入量：１０μＬ
　　試料濃度：０．２ｗ／ｖ％　ＨＰＬＣグレードクロロホルム溶液
　　溶媒流速：０．３５ｍｌ／ｍｉｎ
　　測定温度：４０℃
　　検出器：ＲＩ <Measurement method of weight average molecular weight (Mw)>
The polystyrene-converted weight average molecular weight was determined from the calibration curve of standard polystyrene prepared in advance. That is, a calibration curve was created using standard polystyrene ("PStQuick MP-M" manufactured by Tosoh Corporation) of known molecular weight (molecular weight distribution = 1), and the elution time and molecular weight value of each peak were plotted from the measured standard polystyrene. Then, approximation was performed by a cubic equation to obtain a calibration curve. Mw was calculated by the following calculation formula.
Mw=Σ(Wi×Mi)÷Σ(Wi)
Here, i represents the i-th division point when the molecular weight M is divided, Wi represents the i-th weight, and Mi represents the i-th molecular weight. The molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve. HLC-8320GPC manufactured by Tosoh Corporation was used as a GPC device, one TSKguardcolumn SuperMPHZ-M was used as a guard column, and three TSKgel SuperMultiporeHZ-M were connected in series as an analytical column. Other conditions are as follows.
Solvent: HPLC grade tetrahydrofuran Injection volume: 10 μL
Sample concentration: 0.2 w/v% HPLC grade chloroform solution Solvent flow rate: 0.35 ml/min
Measurement temperature: 40°C
Detector: RI
＜屈折率（ｎＤ、νｄ）の測定方法＞
　得られた樹脂を、４０φ、３ｍｍ厚の円板にプレス成形（成形条件：２００℃、１００ｋｇｆ／ｃｍ２、２分）し、直角に切り出し、カルニュー製ＫＰＲ-２００により２５℃で測定波長５８９ｎｍの屈折率を測定した。 <Method of measuring refractive index (nD, νd)>
The obtained resin was press-molded into a disc having a diameter of 40 mm and a thickness of 3 mm (molding condition: 200° C., 100 kgf/cm 2 , 2 minutes), cut out at a right angle, and measured at a wavelength of 589 nm at 25° C. by KPR-200 manufactured by Kalnew. The refractive index was measured.
＜ＹＩ値の測定方法＞
　得られた樹脂６ｇを６０ｍｌの塩化メチレンに溶解し、光路長６ｃｍのセルにて、分光式色差計（日本電色工業社製、商品名「ＳＥ－２０００」）を用い、ＪＩＳ　７３７３に基づきＹＩ値を測定した。 <Method of measuring YI value>
6 g of the obtained resin was dissolved in 60 ml of methylene chloride, and a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “SE-2000”) was used in a cell with an optical path length of 6 cm to obtain YI based on JIS 7373. The value was measured.
（実施例１）
　下記構造式で表される２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチル（以下、「ＢＩＮＯＬ－ＤＣ」と呼ぶ）５０．２９ｇ（０．１２ｍｏｌ）、下記構造式で表される２，２’－ビス（２－ヒドロキシエトキシ）－６，６’ジフェニル－１，１’－ビナフタレン（以下、「ＤＰ－ＢＨＢＮＡ」と呼ぶ）５２．６６ｇ（０．１０ｍｏｌ）、エチレングリコール（以下、「ＥＧ」と呼ぶ）３．４９ｇ（０．０６ｍｏｌ）、及び触媒としてテトラブトキシチタン０．０１１ｇを撹拌器および留出装置付きの反応釜に入れ、窒素雰囲気常圧下、１８０℃に加熱し、３０分間撹拌した。その後、２５０℃、０．１３ｋＰａ以下まで昇温、減圧することにより重合反応を行った。内容物を反応器から取り出し、ポリエステル樹脂を得た。
　得られたポリエステル樹脂をＮＭＲにより分析した結果、ポリエステル樹脂に導入されたジオール成分の80モル％がＤＰ－ＢＨＢＮＡ由来、２０モル％がＥＧ由来であり、ポリエステル樹脂に導入されたカルボン酸成分の１００モル％がＢＩＮＯＬ－ＤＣ由来であった。ＮＭＲの測定結果を図１に示す。得られたポリエステルの樹脂の物性を表２に示す。 (Example 1)
2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl (hereinafter referred to as “BINOL-DC”) 50.29 g (0.12 mol) represented by the following structural formula, represented by the following structural formula 2,2′-bis(2-hydroxyethoxy)-6,6′diphenyl-1,1′-binaphthalene (hereinafter referred to as “DP-BHBNA”) 52.66 g (0.10 mol), ethylene glycol ( Hereinafter, referred to as “EG”) 3.49 g (0.06 mol) and 0.011 g of tetrabutoxytitanium as a catalyst were placed in a reaction kettle equipped with a stirrer and a distillation device, and heated to 180° C. under a nitrogen atmosphere normal pressure. , Stirred for 30 minutes. Then, the polymerization reaction was carried out by raising the temperature to 250° C. and 0.13 kPa or less and reducing the pressure. The contents were taken out of the reactor to obtain a polyester resin.
As a result of analyzing the obtained polyester resin by NMR, 80 mol% of the diol component introduced into the polyester resin was derived from DP-BHBNA and 20 mol% was derived from EG, and 100% of the carboxylic acid component introduced into the polyester resin was obtained. Mol% was derived from BINOL-DC. The measurement result of NMR is shown in FIG. Table 2 shows the physical properties of the obtained polyester resin.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（実施例２）
　ロットの異なる２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルを用いた以外は、実施例１と同様にしてポリエステル樹脂を得た。得られたポリエステルの樹脂の物性を表２に示す。なお、表２では、実施例１で用いた２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルをＢＩＮＯＬ－ＤＣ－Ａとし、実施例２で用いた２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルをＢＩＮＯＬ－ＤＣ－Ｂとした。 (Example 2)
A polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl of different lots was used. Table 2 shows the physical properties of the obtained polyester resin. In Table 2, 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl used in Example 1 was designated as BINOL-DC-A, and 2,2′-bis used in Example 2 was used. (Hydroxycarbonylmethoxy)-1,1'-binaphthyl was designated as BINOL-DC-B.
（実施例３）
　更にロットの異なる２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルを用いた以外は、実施例１と同様にしてポリエステル樹脂を得た。得られたポリエステルの樹脂の物性を表２に示す。なお、表２では、実施例３で用いた２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルをＢＩＮＯＬ－ＤＣ－Ｃとした。 (Example 3)
Further, a polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl of different lot was used. Table 2 shows the physical properties of the obtained polyester resin. In Table 2, 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl used in Example 3 was designated as BINOL-DC-C.
（実施例４）
　実施例１で用いた２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチル（ＢＩＮＯＬ－ＤＣ－Ａ）５０．２９ｇ（０．１２ｍｏｌ）、下記構造式で表される９，９’－ビス（４－（２－ヒドロキシエトキシ）フェニル）フルオレン（ＢＰＥＦ）１６４．４１ｇ（０．３７ｍｏｌ）、ジフェニルカーボネート５５．９５ｇ（０．２６ｍｏｌ）、及び触媒としてテトラブトキシチタン０．０１５ｇを撹拌器および留出装置付きの反応釜に入れ、窒素雰囲気常圧下、１８０℃に加熱し、３０分間撹拌した。その後、１時間かけて２５５℃、０．１３ｋＰａまで昇温、減圧し、引き続き２５５℃、０．１３ｋＰａで１時間撹拌を続け、重合反応を行った。内容物を反応器から取り出し、ポリエステルカーボネート樹脂を得た。得られたポリエステルカーボネート樹脂の物性を表２に示す。
Figure JPOXMLDOC01-appb-C000016
 (Example 4)
2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl (BINOL-DC-A) 50.29 g (0.12 mol) used in Example 1, represented by the following structural formula 9,9 '-Bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) 164.41 g (0.37 mol), diphenyl carbonate 55.95 g (0.26 mol) and 0.015 g of tetrabutoxy titanium as a catalyst Then, the mixture was placed in a reaction kettle equipped with a distillation device, heated to 180° C. under a nitrogen atmosphere at atmospheric pressure, and stirred for 30 minutes. Thereafter, the temperature was raised to 255° C. and 0.13 kPa over 1 hour, the pressure was reduced, and the mixture was continuously stirred at 255° C. and 0.13 kPa for 1 hour to carry out a polymerization reaction. The contents were taken out of the reactor to obtain a polyester carbonate resin. Table 2 shows the physical properties of the obtained polyester carbonate resin.
Figure JPOXMLDOC01-appb-C000016
（比較例）
　下記表２に示す金属量を含む２，２’－ビス（ヒドロキシカルボニルメトキシ）－１，１’－ビナフチルを用いた以外は、実施例１と同様にしてポリエステル樹脂を得た。得られたポリエステルの樹脂の物性を表２に示す。 (Comparative example)
A polyester resin was obtained in the same manner as in Example 1 except that 2,2′-bis(hydroxycarbonylmethoxy)-1,1′-binaphthyl containing the amount of metal shown in Table 2 below was used. Table 2 shows the physical properties of the obtained polyester resin.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
  本発明の熱可塑性樹脂は、高屈折率、高耐熱性及び低ＹＩ値を有するため、光ディスク、透明導電性基板、光カード、シート、フィルム、光ファイバー、レンズ、プリズム、光学膜、基盤、光学フィルター、ハードコート膜等の光学部材に用いることができ、特に、スマートフォン、ＤＳＣ、車載などのカメラ用レンズに極めて有用である。本発明の熱可塑性樹脂を用いることにより、望遠等に用いられるレンズユニットの薄型化を図ることが可能となる。
  Since the thermoplastic resin of the present invention has a high refractive index, high heat resistance and low YI value, it is an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a substrate, an optical filter. It can be used as an optical member such as a hard coat film, and is particularly useful as a lens for a camera such as a smartphone, a DSC, and a vehicle. By using the thermoplastic resin of the present invention, it is possible to reduce the thickness of the lens unit used for telephoto and the like.

Claims (9)

  1. 　少なくとも、下記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物を反応させて熱可塑性樹脂を製造する方法であって、
    　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含む、製造方法。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ａおよびｂは、それぞれ独立して０～５の整数を表す。）     A method for producing a thermoplastic resin by reacting at least a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid,
    The manufacturing method, wherein the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and a and b each independently represent an integer of 0 to 5.)
  2. 　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、Zn及びSnを合計で５４ｐｐｂ以上の量で含む、請求項１に記載の製造方法。 The manufacturing method according to claim 1, wherein the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 54 ppb or more.
  3. 　前記金属が、Feを２０～３０００ｐｐｂの量で含む、請求項１または２に記載の製造方法。 The manufacturing method according to claim 1 or 2, wherein the metal contains Fe in an amount of 20 to 3000 ppb.
  4. 　前記金属が、Liを１～１００ｐｐｂ、Naを２～５００ｐｐｂ、Mgを１～１０００ｐｐｂ、Alを５～５００ｐｐｂ、Kを２０～３０００ｐｐｂ、Caを５～１０００ｐｐｂ、Tiを１～１００ｐｐｂ、Crを５～５００ｐｐｂ、Niを１～１００ｐｐｂ、Znを２～１００ｐｐｂ、Sn を１～１００ｐｐｂの量で含む、請求項１～３のいずれか一項に記載の製造方法。 The metal is 1 to 100 ppb for Li, 2 to 500 ppb for Na, 1 to 1000 ppb for Mg, 5 to 500 ppb for Al, 20 to 3000 ppb for K, 5 to 1000 ppb for Ca, 1 to 100 ppb for Ti, 5 to 5 pp for Cr. The production method according to any one of claims 1 to 3, which comprises 500 ppb, 1 to 100 ppb of Ni, 2 to 100 ppb of Zn, and 1 to 100 ppb of Sn.
  5. 　前記式（１）で表されるジカルボン酸および該ジカルボン酸に由来する金属を含有する組成物に、下記式（２）で表されるジオール化合物を反応させる、請求項１～４のいずれか一項に記載の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     （式（２）中、Ｒ３およびＲ４は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ｃおよびｄは、それぞれ独立して０～５の整数を表す。）     5. The composition containing a dicarboxylic acid represented by the formula (1) and a metal derived from the dicarboxylic acid is reacted with a diol compound represented by the following formula (2). The manufacturing method according to item.
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (2), R 3 and R 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and c and d each independently represent an integer of 0 to 5.)
  6. 　前記熱可塑性樹脂が、ポリエステルまたはポリエステルカーボネートである、請求項１～５のいずれか一項に記載の製造方法。 The method according to any one of claims 1 to 5, wherein the thermoplastic resin is polyester or polyester carbonate.
  7. 　下記式（３）で表される構成単位と、該構成単位を構成するジカルボン酸に由来する金属とを含む熱可塑性樹脂であって、
    　前記金属が、Li、Na、Mg、Al、K、Ca、Ti、Cr、Fe、Ni、ZnおよびSnを合計で１００００ｐｐｂ以下の量で含む、熱可塑性樹脂。
    Figure JPOXMLDOC01-appb-C000003
     （式（３）中、Ｒ５およびＲ６は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１～６のアルキル基、または、Ｏ、Ｎ及びＳから選択されるヘテロ環原子を含んでいてもよい炭素数６～２０のアリール基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、もしくは炭素数７～１７のアラルキル基を表す。ｅおよびｆは、それぞれ独立して０～５の整数を表す。）     A thermoplastic resin comprising a structural unit represented by the following formula (3) and a metal derived from a dicarboxylic acid constituting the structural unit:
    A thermoplastic resin in which the metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn in a total amount of 10,000 ppb or less.
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (3), R 5 and R 6 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or O, N and S. An aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, which may contain a heterocyclic atom selected from Represents, and e and f each independently represent an integer of 0 to 5.)
  8. 　前記熱可塑性樹脂が７～４０のＹＩ値を有する、請求項７に記載の熱可塑性樹脂。 The thermoplastic resin according to claim 7, wherein the thermoplastic resin has a YI value of 7 to 40.
  9. 　請求項７または８に記載の熱可塑性樹脂を含む、光学レンズ。
          An optical lens comprising the thermoplastic resin according to claim 7.
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