WO2020137927A1 - 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 - Google Patents

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 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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carbon atoms
ppb
thermoplastic resin
atom
dicarboxylic acid
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PCT/JP2019/050234
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English (en)
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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Priority to JP2020563228A priority Critical patent/JP7548015B2/ja
Priority to KR1020217013301A priority patent/KR20210108943A/ko
Priority to CN201980085972.6A priority patent/CN113260883A/zh
Publication of WO2020137927A1 publication Critical patent/WO2020137927A1/ja
Priority to JP2024058426A priority patent/JP2024079821A/ja

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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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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyesters Or Polycarbonates (AREA)
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CN201980085972.6A CN113260883A (zh) 2018-12-28 2019-12-23 热塑性树脂及其制造方法和包含该热塑性树脂的光学透镜
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