WO2018008483A1 - Résine thermoplastique - Google Patents

Résine thermoplastique Download PDF

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Publication number
WO2018008483A1
WO2018008483A1 PCT/JP2017/023665 JP2017023665W WO2018008483A1 WO 2018008483 A1 WO2018008483 A1 WO 2018008483A1 JP 2017023665 W JP2017023665 W JP 2017023665W WO 2018008483 A1 WO2018008483 A1 WO 2018008483A1
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Prior art keywords
thermoplastic resin
carbon atoms
general formula
atom
hydrocarbon group
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PCT/JP2017/023665
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English (en)
Japanese (ja)
Inventor
敬介 佐藤
学 松井
和徳 布目
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帝人株式会社
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Priority claimed from JP2016132161A external-priority patent/JP6689146B2/ja
Priority claimed from JP2016132160A external-priority patent/JP6739255B2/ja
Priority claimed from JP2016132162A external-priority patent/JP6689147B2/ja
Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to CN201780041615.0A priority Critical patent/CN109415500B/zh
Priority to KR1020197000814A priority patent/KR102245600B1/ko
Publication of WO2018008483A1 publication Critical patent/WO2018008483A1/fr

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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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

Definitions

  • the present invention relates to a thermoplastic resin and an optical lens. More specifically, the present invention relates to a thermoplastic resin having a specific ester structure having a high refractive index, low birefringence and high heat resistance in a well-balanced manner, and an optical lens comprising the same.
  • Optical glass or optical transparent 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, and the like, but has 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 resin, etc. are used as high refractive index materials for camera lenses.
  • a resin having a high refractive index has been demanded due to the lighter, thinner and smaller products.
  • a lens element having the same refractive index can be realized on a surface with a smaller curvature. Therefore, the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, It becomes possible to reduce the polarization sensitivity and reduce the thickness by reducing the lens thickness.
  • Patent Document 1 includes, as a monomer component, a biaryl compound that is bonded with a bond axis that can impart internal rotational isomerism, and at least one aryl group has 4n + 6 (n is a natural number) with respect to the bond axis.
  • a resin composition is disclosed, having excellent transparency, low optical anisotropy, high refractive index, low moisture absorption, etc. An optical lens material having refraction has not yet been obtained.
  • a first object of the present invention is to provide a thermoplastic resin having a high refractive index, a low birefringence and a high heat resistance, and particularly excellent in optical properties.
  • the second object of the present invention is to provide a thermoplastic resin excellent in optical properties having a particularly high balance of refractive index and heat resistance in addition to the above first object.
  • the third object is to provide a thermoplastic resin excellent in optical characteristics having a particularly high heat resistance in addition to the above first object.
  • the fourth object is to provide a thermoplastic resin excellent in optical properties, which has a particularly high refractive index in addition to the first object.
  • thermoplastic resins represented by the following general formula (1) and the following general formula (2) As a result of intensive research aimed at achieving this object, the present inventors have found that the above problems can be solved by the thermoplastic resins represented by the following general formula (1) and the following general formula (2).
  • the present invention has been reached.
  • thermoplastic resin containing 70 mol% or more of the total repeating units represented by the following general formula (1) and the following general formula (2).
  • R 1 and R 2 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms
  • n and m each independently represents an integer of 0 or more
  • R 3 to R 10 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 11 and R 12 are each independently represents an even better hydrocarbon group containing an aromatic group of carbon atoms 1 ⁇ 10, o and p are .R 13 and represent an integer of 0 or greater each independently R 14 each independently represents a hydrogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 20 carbon atoms.)
  • R 1 and R 2 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms
  • n and m each independently represents an integer of 0 or more.
  • R 3 to R 10 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 15 and R 16 each independently represents a hydrocarbon group which may include an aromatic group having a carbon number of 1 ⁇ 10, q and r is an each independently an integer of 0 or more .
  • R 17 ⁇ R 24 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms.) 2.
  • R 11 and R 12 are each a hydrocarbon group having 1 to 4 carbon atoms, o and p are each 0 or 1, and R 13 and R 14 are each hydrogen. 2.
  • thermoplastic resin as described in 1 above which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms. 3.
  • R 11 and R 12 are each an ethylene group
  • o and p are each 1
  • R 13 and R 14 are each a hydrogen atom or a phenyl group.
  • R 15 and R 16 are each a hydrocarbon group having 1 to 4 carbon atoms
  • q and r are each 0 or 1
  • R 17 to R 24 are each hydrogen.
  • R 1 and R 2 are each a hydrocarbon group having 1 to 3 carbon atoms, n and m are each 0 or 1, and R 3 2.
  • R 1 and R 2 are each a methylene group, n and m are each 1, and R 3 to R 10 are hydrogen atoms.
  • thermoplastic resin as described in any one of 1 to 10 above which has a glass transition temperature of 128 to 160 ° C. 14 11.
  • thermoplastic resin of the present invention has a high refractive index, a low birefringence and a high heat resistance, the industrial effect is particularly remarkable.
  • FIG. 1 is a proton NMR of the polyester carbonate resin obtained in Example 12.
  • FIG. 2 is a proton NMR of the polyester resin obtained in Example 21.
  • thermoplastic resin of the present invention will be described in more detail.
  • Embodiment [1] of the present invention will be described.
  • Embodiment [1] of the present invention is a thermoplastic resin in which the total of repeating units represented by the following general formula (1) and the following general formula (2) is 70 mol% or more of all units.
  • thermoplastic resin of the present invention needs to contain 70 mol% or more of repeating units represented by the following general formula (1) and the following general formula (2), preferably 75 mol% or more, more preferably 80 mol%. % Or more. Within this range, the heat resistance is excellent.
  • the 1,1′-binaphthyl skeleton improves the heat resistance and refractive index of the thermoplastic resin, and is orthogonal to the bond axis connecting two naphthalene rings. Because of its conformation, it has the effect of reducing birefringence.
  • the 1,1′-binaphthyl skeleton may be substituted with a substituent or may be condensed with each other.
  • substituents are exemplified and are not particularly limited, but typically, alkyl, aryl and the like can be mentioned.
  • the alkyl group preferably has 1 to 12 carbon atoms and may be linear or branched.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group.
  • the binaphthyl skeleton may be any of R, S and racemates, and preferably a racemate. Racemates that do not require optical resolution have a cost advantage.
  • 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 effects of the present invention.
  • R 1 and R 2 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represents 0 or more. Indicates an integer.
  • R 3 to R 10 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 11 and R 12 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and o and p each independently represent an integer of 0 or more.
  • R 13 and R 14 each independently represent a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 20 carbon atoms.
  • R 1 and R 2 are preferably each independently a hydrocarbon group having 1 to 3 carbon atoms, and n and m are preferably each independently an integer of 0 or 1.
  • R 3 to R 10 are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 11 and R 12 are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, o and p are each independently an integer of 0 or 1, and R 13 and R 14 are Each independently represents a hydrocarbon group which may contain a hydrogen atom or an aromatic group having 1 to 12 carbon atoms.
  • R 1 and R 2 represent a methylene group
  • n and m represent 1
  • R 3 to R 10 represent a hydrogen atom
  • R 11 and R 12 represent an ethylene group
  • R 13 and R 14 represent a hydrogen atom or a phenyl group.
  • R 1 and R 2 may be the same or different, n and m may be the same or different, and R 3 to R 10 may be the same or different.
  • R 11 and R 12 may be the same or different, o and p may be the same or different, and R 13 and R 14 may be the same or different. May be.
  • R 1 and R 2 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represents 0 or more. Indicates an integer.
  • R 3 to R 10 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 15 and R 16 each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and q and r each independently represents an integer of 0 or more.
  • R 17 to R 24 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 1 and R 2 are preferably each independently a hydrocarbon group having 1 to 3 carbon atoms, and n and m are preferably each independently an integer of 0 or 1.
  • R 3 to R 10 are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 15 and R 16 are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, and q and r are preferably each independently an integer of 0 or 1.
  • R 17 to R 24 are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 1 and R 2 represent a methylene group
  • n and m represent 1
  • R 3 to R 10 represent a hydrogen atom
  • R 15 and R 16 represent an ethylene group
  • R 17 to R 24 represent a hydrogen atom.
  • R 1 and R 2 may be the same or different, n and m may be the same or different, and R 3 to R 10 may be the same or different.
  • R 15 and R 16 may be the same or different, q and r may be the same or different, and R 17 to R 24 may be the same or different. May be.
  • the first object of the present invention is to provide a high refractive index and high heat resistance, and the refractive index at a measurement wavelength of 589 nm (hereinafter sometimes abbreviated as nD) at 25 ° C. is 1.650 to 1.700. It is preferably 1.65 to 1.695, more preferably 1.657 to 1.686.
  • the glass transition point (hereinafter sometimes abbreviated as Tg) is preferably 128 to 160 ° C., and more preferably 130 to 158 ° C.
  • the specific viscosity of the thermoplastic resin of the present invention is preferably from 0.12 to 0.40, more preferably from 0.15 to 0.35, and even more preferably from 0.18 to 0.30.
  • the specific viscosity is preferably in the above range because the balance between moldability and mechanical strength is excellent. Most preferably, it is 0.26 to 0.27.
  • the Abbe number ( ⁇ ) of the thermoplastic resin of the present invention is preferably 17 to 25, and more preferably 17 to 23.
  • the Abbe number is calculated from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm measured at 25 ° C. using the following formula.
  • nD refractive index at a wavelength of 589 nm
  • nC refractive index at a wavelength of 656 nm
  • nF Refractive index at a wavelength of 486 nm.
  • the thermoplastic resin of the present invention preferably has an absolute value of orientation birefringence ( ⁇ n) calculated by the following formula of 0 to 4 ⁇ 10 ⁇ 3 , more preferably 0 to 2 ⁇ 10 ⁇ 3 . is there.
  • the orientation birefringence ( ⁇ n) is measured at a wavelength of 589 nm when a 100 ⁇ m-thick cast film obtained from the thermoplastic resin of the present invention is stretched twice at Tg + 10 ° C. It is preferable that the orientation birefringence is within the above range because the optical distortion of the lens becomes small.
  • ⁇ n Re / d ⁇ n: orientation birefringence
  • Re phase difference (nm)
  • d Thickness (nm)
  • the repeating units of the general formula (1) and the general formula (2) can be produced by reacting a diol component and a dicarboxylic acid component described later.
  • Dicarboxylic acid component of general formula (1) and general formula (2) As the dicarboxylic acid component, a compound represented by the following formula (a) or an ester-forming derivative thereof is mainly preferably used.
  • R 1 and R 2 are each independently of 1 to 10 carbon atoms.
  • the hydrocarbon group which may contain an aromatic group is shown, n and m show an integer greater than or equal to 0 each independently.
  • R 3 to R 10 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 1 and R 2 are preferably each independently a hydrocarbon group having 1 to 3 carbon atoms, and n and m are preferably each independently an integer of 0 or 1.
  • R 3 to R 10 are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R 1 and R 2 represent a methylene group, n and m represent 1, and R 3 to R 10 represent a hydrogen atom. Further, R 1 and R 2 may be the same or different, n and m may be the same or different, and R 3 to R 10 may be the same or different. Also good.
  • dicarboxylic acid represented by the general formula (a) or an ester-forming derivative thereof will be shown.
  • R 11 and R 12 are each independently a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms. O and p each independently represent an integer of 0 or more.
  • R 13 and R 14 each independently represent a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 20 carbon atoms.
  • R 11 and R 12 are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, and o and p are each independently an integer of 0 or 1. Particularly preferably, R 11 and R 12 represent an ethylene group, o and p represent 1, and R 13 and R 14 represent a hydrogen atom or a phenyl group. Further, R 11 and R 12 may be the same or different, o and p may be the same or different, and R 13 and R 14 may be the same or different. May be.
  • R 15 and R 16 each independently represents a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms.
  • Q and r each independently represents an integer of 0 or more.
  • R 17 to R 24 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.
  • R 15 and R 16 each preferably represents a hydrocarbon group having 1 to 4 carbon atoms, and q and r each preferably represents an integer of 0 or 1.
  • R 17 to R 24 are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R 15 and R 16 represent an ethylene group, q and r represent 1, and R 17 to R 24 represent a hydrogen atom. Furthermore, R 15 and R 16 may be the same or different, o and p may be the same or different, and R 17 to R 24 may be the same or different. Also good.
  • thermoplastic resin in the present invention has a repeating unit represented by the general formula (1) and the general formula (2), but may contain a copolymer component separately.
  • copolymer component examples include dicarboxylic acid components other than those represented by the general formula (a), diol components other than the compounds represented by the general formula (b) and the general formula (c), and repeating units having a carbonate bond. Is exemplified.
  • dicarboxylic acid component as a copolymerization component examples include aliphatic dicarboxylic acid components such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, 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
  • alicyclic dicarboxylic acid component You may use these individually or in combination of 2 or more types.
  • acid chlorides and esters may be used as these derivatives.
  • a monocyclic aromatic dicarboxylic acid component, a polycyclic aromatic dicarboxylic acid component, and a biphenyl dicarboxylic acid component are preferable because the heat resistance and the refractive index are easily increased.
  • diol component as the copolymer component examples include aliphatic diol components such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol, and tricyclo [5.2.
  • decane dimethanol cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, 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-hydroxy Phenyl) -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)
  • the diol component exemplified in the general formula (b) and the general formula (c) and the diol component exemplified as the copolymer component are carbonated.
  • 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, biscresol fluorene, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl, 1,1′-bi -2-Naphthol is preferred.
  • thermoplastic resin of the present invention is obtained by subjecting the raw materials represented by the general formulas (a), (b) and (c) to an esterification reaction or an ester exchange reaction, and subjecting the obtained reaction product to a polycondensation reaction
  • a diol component and a dicarboxylic acid component or a diester thereof are mixed and reacted under reduced pressure usually at 120 to 350 ° C., preferably 150 to 300 ° C. .
  • the degree of vacuum 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.
  • a polymerization catalyst known per se can be employed as the polymerization catalyst, and for example, an antimony compound, a titanium compound, a germanium compound, a tin compound, or an aluminum compound is preferable.
  • tin, titanium, and a germanium compound are preferable from the viewpoint of melt stability of the thermoplastic resin and hue.
  • a catalyst known per se can be employed.
  • 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.
  • compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, alcoholates and the like are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and a small amount of polymer-insoluble foreign matter.
  • manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more.
  • the amount of the catalyst used is, for example, about 0.01 ⁇ 10 ⁇ 4 to 100 ⁇ 10 ⁇ 4 mol, preferably about 0.1 ⁇ 10 ⁇ 4 to 40 ⁇ 10 ⁇ 4 mol, relative to 1 mol of the dicarboxylic acid component. There may be.
  • the thermoplastic resin of the present invention may contain a copolymer component other than the repeating unit of the general formula (1) and the general formula (2).
  • a copolymer component other than the repeating unit of the general formula (1) and the general formula (2).
  • it when using it as a polyester carbonate resin, it can manufacture by making it react with dicarboxylic acid chloride and phosgene other than a diol component and a dicarboxylic acid component, or making a diol, dicarboxylic acid, and biaryl carbonate react.
  • 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 still more preferably less than 20 mol% with respect to 100 mol% of the dicarboxylic acid component.
  • the ratio of the units represented by the general formula (1) and the general formula (2) is preferably 20 to 80:80 to 20, more preferably 25 to 75. : 75 to 25, more preferably 30 to 70: 70 to 30.
  • the second object of the present invention is to provide a particularly high refractive index and heat resistance in a well-balanced manner.
  • ND is 1.665 to 1.680
  • Tg is More preferably, the temperature is 138 to 150 ° C., more preferably nD is 1.668 to 1.679, and Tg is 140 to 147 ° C.
  • high refractive index, low birefringence and high heat resistance can be achieved, and in particular, high refractive index and heat resistance can be provided in a well-balanced manner.
  • the repeating unit represented by the general formula (1) is preferably 70 mol% or more, more preferably 75 mol% or more, further preferably 80 mol% or more in all repeating units. . Within this range, the heat resistance is excellent.
  • the 1,1′-binaphthyl skeleton improves the heat resistance and refractive index of the thermoplastic resin and has a conformation that is orthogonal to the bond axis connecting two naphthalene rings. Therefore, there is an effect of reducing birefringence.
  • thermoplastic resin a polyester resin or a polyester carbonate resin is preferable, and a polyester resin is particularly preferable from the viewpoint of the effect of the present invention.
  • the third object of the present invention is to provide a particularly high heat resistance in addition to the first object, and Tg is 144 to 158 and nD is 1.657 to 1.673. More preferably, Tg is 150 to 155 ° C. and nD is most preferably 1.659 to 1.673.
  • Tg and nD are within the above ranges because in addition to high refractive index and low birefringence, the balance between heat resistance and moldability is further excellent.
  • the repeating unit represented by the general formula (2) is preferably 70 mol% or more of the whole, more preferably 75 mol% or more, and further preferably 80 mol% or more. Within this range, the balance between heat resistance and moldability is excellent.
  • the 1,1′-binaphthyl skeleton has a conformation that improves the heat resistance and refractive index of the thermoplastic resin and is orthogonal to the bond axis connecting two naphthalene rings. Therefore, there is an effect of reducing birefringence.
  • thermoplastic resin a polyester resin or a polyester carbonate resin is preferable, and a polyester resin is particularly preferable from the viewpoint of the effect of the present invention.
  • the fourth object of the present invention is to provide a particularly high refractive index in addition to the first object, more preferably nD is 1.675 to 1.690, and Tg is More preferably, it is 130 to 143 ° C., more preferably nD is 1.679 to 1.682, and Tg is 130 to 137 ° C.
  • the refractive index is measured at 25 ° C. and wavelength 589 nm.
  • the refractive index is 1.650 or more, further 1.675 or more, particularly 1.777 or more, the spherical aberration of the lens can be reduced, and the focal length of the lens can be further shortened.
  • additives such as a heat stabilizer, an antioxidant, a mold release agent, a plasticizer, a filler, and an ultraviolet absorber as necessary to obtain a thermoplastic resin composition. Can be used.
  • ester of alcohol and fatty acid examples include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid.
  • the monohydric alcohol and fatty acid ester is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
  • the partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
  • monohydric alcohol, saturated fatty acid and ester examples include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, and stearyl stearate is preferable.
  • partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or parts of dipentaerythritol, such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include esters.
  • 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, and more preferably 95% by weight or more when the release agent is 100% by weight.
  • the mold release agent to be blended in the thermoplastic resin composition is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • the range of 0.02 to 0.5 parts by weight is more preferable.
  • heat stabilizers examples include phosphorus heat stabilizers, sulfur heat stabilizers, and hindered phenol heat stabilizers.
  • the phosphorus heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples thereof include triphenyl phosphite and tris (nonylphenyl) phosphite.
  • tris (2,4-di-tert-butylphenyl) phosphite tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite
  • 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.
  • the hindered phenol heat stabilizer is preferably triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydroxy Namide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl este
  • the content of the hindered phenol heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • Preferred sulfur-based heat stabilizers are pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropioate).
  • the thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), etc., and can be easily used.
  • the content of the sulfur-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight with respect to parts by weight of the thermoplastic resin composition.
  • the UV absorber at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.
  • benzotriazole type ultraviolet absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1 , 1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, -(2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-oct
  • 2- (2-hydroxy-5-methylphenyl) benzotriazole 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dic Milphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazo- And particularly preferably 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2, '- methylenebis [4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotria
  • benzophenone ultraviolet absorber 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetra Hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-) 2-methoxyph ) Methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone.
  • 2,2′-bis (3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazine-4-one) are preferable.
  • Such a compound is commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and can be easily used.
  • 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3) is preferable.
  • Examples include -diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. More preferred is 2,2′-p-phenylenebis (3,1-benzoxazin-4-one).
  • 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. Sufficient weather resistance can be imparted.
  • the thermoplastic resin of the present invention is suitable for optical members, particularly optical lenses.
  • the thermoplastic optical lens of the present invention is manufactured by injection molding, it is preferably molded under 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 conditions of a cylinder temperature of 270 to 320 ° C. and a mold temperature of 100 to 160 ° C.
  • the cylinder temperature is higher than 350 ° C.
  • the thermoplastic resin is decomposed and colored, and when 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 is difficult to take out a molded piece made of a thermoplastic resin from the mold.
  • the mold temperature is less than 90 ° C., the resin hardens too quickly in the mold during molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Tends to be difficult.
  • the optical lens of the present invention is preferably implemented using an aspherical lens shape as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, it is not necessary to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing molding costs. It becomes 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 having a thin, small and complicated shape.
  • the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and still more preferably 0.1 to 2.0 mm.
  • the diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and still more preferably 3.0 to 10.0 mm.
  • it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.
  • the lens made of the thermoplastic resin in the optical lens of the present invention is molded by an arbitrary method such as mold forming, cutting, polishing, laser processing, electric discharge processing, and etching. Among these, die molding is more preferable from the viewpoint of manufacturing cost.
  • thermoplastic resin in which the total of the repeating units represented by the general formula (1) and the following general formula (2) is 70 mol% or more in all units was performed by the following method.
  • Refractive index (nd) The refractive index (wavelength: 589 nm) at 25 ° C. of the film prepared by the method of (a) was measured using an Abbe refractometer of DR-M2 manufactured by ATAGO.
  • Oriented birefringence ( ⁇ n) A cast film having a thickness of 100 ⁇ m prepared by the method of (a) was stretched twice at Tg + 10 ° C., and the position at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The phase difference (Re) was measured, and the orientation birefringence ( ⁇ n) was determined from the following formula.
  • ⁇ n Re / d ⁇ n: orientation birefringence
  • Re phase difference (nm)
  • d Thickness (nm) ⁇ : 0 or more, 2 ⁇ 10 ⁇ 3 or less ⁇ : 2 ⁇ 10 ⁇ 3 or more, 4 ⁇ 10 ⁇ 3 or less ⁇ : 4 ⁇ 10 ⁇ 3 or more
  • Example of Embodiment [1] [2] of the present invention 1 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl (BCMB) 16.90 parts by weight, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) 12.72 parts by weight Parts, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl (BHEB) 10.86 parts by weight, diphenyl carbonate (DPC) 3.64 parts by weight, and tetrabutoxytitanium 17.0 ⁇ 10 ⁇ 3 parts by weight were placed in
  • the dicarboxylic acid component introduced into the polyester resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 58 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 29 mol% was derived from BPEF, and 29 mol% was derived from BHEB.
  • the obtained polyester resin had a specific viscosity of 0.26, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.669.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BPEF was 10.96 parts by weight, BHEB was 9.36 parts by weight, and DPC was 0 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 25 mol% was derived from BPEF, and 25 mol% was derived from BHEB.
  • Example 3 Polymerization was conducted in the same manner as in Example 1 except that BCMB was 20.12 parts, BPEF was 10.96 parts, BHEB was 5.62 parts, ethylene glycol (EG) was 3.72 parts, and DPC was 0 parts.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 25 mol% was derived from BPEF, 15 mol% was derived from BHEB, and 10 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.26, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.670.
  • Example 4 BCMB 16.90 parts by weight, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (OPBPEF) 17.13 parts by weight, BHEF 10.86 parts by weight, DPC 3.64 parts by weight was polymerized in the same manner as in Example 1.
  • OPBPEF 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene
  • the dicarboxylic acid component introduced into the polyester resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 58 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 29 mol% was derived from OPBPEF, and 29 mol% was derived from BHEB.
  • the specific viscosity of the obtained polyester resin was 0.27
  • the glass transition temperature Tg was 144 ° C.
  • the refractive index was 1.673.
  • Example 5 Polymerization was conducted in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, OPBPEF was 14.77 parts by weight, BHEB was 9.36 parts by weight, and DPC was 0 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 25 mol% was derived from OPBPEF, and 25 mol% was derived from BHEB.
  • Example 6 Polymerization was conducted in the same manner as in Example 1 except that BCMB was 20.12 parts, OPBPEF was 11.81 parts, BHEB was 7.49 parts, ethylene glycol (EG) was 3.72 parts, and DPC was 0 parts.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 20 mol% was derived from OPBPEF, 20 mol% was derived from BHEB, and 10 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.675.
  • Example 7 Example 1 except that 20.93 parts by weight of 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl (BECMB), 10.96 parts by weight of BPEF, 9.36 parts by weight of BHEB, and 0 parts by weight of DPC was polymerized in the same manner.
  • the obtained pellet was analyzed by NMR.
  • the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester component + total diol component), and the diol component introduced into the polyester resin was the total monomer.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 30 mol% was derived from BHEB, and 20 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 128 ° C., and a refractive index of 1.777.
  • Comparative Example 2 Polymerization was conducted in the same manner as in Example 1 except that 9.71 parts by weight of dimethyl terephthalate (DMT), 18.72 parts by weight of BHEB, and 0 parts by weight of diphenyl carbonate (DPC) were used. The obtained pellet was analyzed by NMR. As a result, the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester component + total diol component), and the diol component introduced into the polyester resin was the total monomer. It was 50 mol% with respect to the component (total diester component + total diol component).
  • DMT dimethyl terephthalate
  • BHEB BHEB
  • DPC diphenyl carbonate
  • the obtained polyester resin had a specific viscosity of 0.25, a glass transition temperature Tg of 127 ° C., and a refractive index of 1.658.
  • Comparative Example 3 Polymerization was conducted in the same manner as in Example 1 except for 21.93 parts by weight of BPEF, 18.72 parts by weight of BHEB, and 21.85 parts by weight of DPC.
  • the obtained pellet was analyzed by NMR, 50 mol% was derived from BPEF and 50 mol% was derived from BHEB with respect to all monomer components introduced into the polycarbonate resin.
  • the polycarbonate resin obtained had a specific viscosity of 0.23, a glass transition temperature Tg of 135 ° C., and a refractive index of 1.649.
  • Comparative Example 4 Polymerization was conducted in the same manner as in Example 1 except that 43.85 parts by weight of BPEF and 21.85 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, 100 mol% of the diol component introduced into the polycarbonate resin was derived from BPEF. The polycarbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 147 ° C., and a refractive index of 1.638.
  • the value of the formula (1) + the formula (2) in Table 1 is the ratio of the repeating units represented by the formula (1) and the formula (2) when the total of all the repeating units is 100 mol%.
  • the polyester or polyester carbonate resin obtained in Examples 1 to 7 in Table 1 is a resin having a high refractive index, low birefringence and high heat resistance, and is excellent as an optical lens.
  • Comparative Example 1 has a high refractive index and low birefringence, but has lower heat resistance than the polymer.
  • Comparative Example 2 birefringence is not sufficiently canceled out, so that the birefringence obtained from the polymer is large and the heat resistance is poor.
  • Comparative Example 3 is a polycarbonate copolymer obtained by copolymerizing 1,1'-binaphthalene structure as a diol component BHEB with BPEF, but its refractive index is lower than that of the polymer.
  • Embodiment 11 of embodiment [1] and [3] of the present invention 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl (BCMB) 16.90 parts by weight, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) 25.43 parts by weight Part, 3.64 parts by weight of diphenyl carbonate (DPC) and 17.0 ⁇ 10 ⁇ 3 parts by weight of tetrabutoxytitanium are placed in a reactor equipped with a stirrer and a distillation apparatus, and heated to 180 ° C. under a nitrogen atmosphere and normal pressure. Stir for 20 minutes.
  • BCMB 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl
  • BPEF 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
  • DPC diphenyl carbonate
  • tetrabutoxytitanium tetra
  • the temperature was gradually raised and reduced, and the temperature was raised and reduced to 260 ° C. and 0.13 kPa or less to conduct a transesterification reaction / polycondensation reaction.
  • the contents were taken out from the reactor to obtain polyester carbonate resin pellets.
  • the dicarboxylic acid component introduced into the polyester carbonate resin was introduced into the polyester carbonate resin in an amount of 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component).
  • the diol component was 58 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component).
  • the polyester carbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 150 ° C., and a refractive index of 1.660.
  • Example 12 Polymerization was conducted in the same manner as in Example 11 except that BCMB was 20.12 parts by weight, BPEF was 21.93 parts by weight, and DPC was 0 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all the monomer components (total dicarboxylic acid component + total diol component).
  • Example 13 Polymerization was conducted in the same manner as in Example 11 except that BCMB was 20.12 parts by weight, BPEF was 17.54 parts by weight, DPC was 0 parts by weight, and ethylene glycol (EG) was 3.72 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 40 mol% was derived from BPEF, and 10 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.24, a glass transition temperature Tg of 145 ° C., and a refractive index of 1.665.
  • Example 14 Example 11 except that 16.90 parts by weight of BCMB, 34.26 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (OPBPEF) and 3.64 parts by weight of DPC were used. Polymerization was carried out in the same manner. The obtained pellets were analyzed by NMR. As a result, the diol acid component introduced into the polyester carbonate resin was 58 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the dicarboxylic acid introduced into the polyester carbonate resin. The component was 42 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component).
  • OPBPEF 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene
  • polyester carbonate resin had a specific viscosity of 0.26, a glass transition temperature Tg of 153 ° C., and a refractive index of 1.668.
  • Example 15 Polymerization was conducted in the same manner as in Example 11 except that BCMB was 20.12 parts by weight, OPBPEF was 29.54 parts by weight, and DPC was 0 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all the monomer components (total dicarboxylic acid component + total diol component).
  • the specific viscosity of the obtained polyester resin was 0.26
  • the glass transition temperature Tg was 153 ° C.
  • the refractive index was 1.671.
  • Example 16 Polymerization was conducted in the same manner as in Example 11 except that BCMB was 20.12 parts by weight, BHEB was 23.63 parts by weight, DPC was 0 parts by weight, and ethylene glycol (EG) was 3.72 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 40 mol% was derived from OPBPEF, and 10 mol% was derived from EG.
  • Example 17 Polymerization was conducted in the same manner as in Example 11 except that 22.93 parts by weight of 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl (BECMB), 21.93 parts by weight of BPEF, and 0 parts by weight of DPC were used.
  • BECMB 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl
  • BPEF BPEF
  • DPC 0 parts by weight
  • Example 11 except that BCMB was 20.12 parts by weight, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl (BHEB) was 11.23 parts by weight, and EG was 4.34 parts by weight. Polymerized.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 30 mol% was derived from BHEB, and 20 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 128 ° C., and a refractive index of 1.777.
  • Comparative Example 12 Polymerization was conducted in the same manner as in Example 11 except that dimethyl terephthalate (DMT) was 9.71 parts by weight, BHEB was 18.72 parts by weight, and diphenyl carbonate (DPC) was 0 parts by weight.
  • the obtained pellet was analyzed by NMR.
  • the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester component + total diol component), and the diol component introduced into the polyester resin was the total monomer. It was 50 mol% with respect to the component (total diester component + total diol component).
  • the obtained polyester resin had a specific viscosity of 0.25, a glass transition temperature Tg of 127 ° C., and a refractive index of 1.658.
  • Comparative Example 13 Polymerization was carried out in the same manner as in Examples except for 21.93 parts by weight of BPEF, 18.72 parts by weight of BHEB, and 21.85 parts by weight of DPC.
  • the obtained pellet was analyzed by NMR, 50 mol% was derived from BPEF and 50 mol% was derived from BHEB with respect to all monomer components introduced into the polycarbonate resin.
  • the polycarbonate resin obtained had a specific viscosity of 0.23, a glass transition temperature Tg of 135 ° C., and a refractive index of 1.649.
  • Comparative Example 14 Polymerization was conducted in the same manner as in Example 11 except that 43.85 parts by weight of BPEF and 21.85 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, 100 mol% of the diol component introduced into the polycarbonate resin was derived from BPEF. The polycarbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 147 ° C., and a refractive index of 1.638.
  • the value of Formula (1) in Table 2 is the ratio of the repeating unit represented by Formula (1) when the total of all repeating units is 100 mol%.
  • the polyester or polyester carbonate resin obtained in Examples 11 to 17 in Table 2 is a resin having high refractive index, low birefringence and high heat resistance, and is excellent as an optical lens.
  • the polymer of Comparative Example 11 has low heat resistance, and Comparative Example 12 does not sufficiently cancel out birefringence and has poor heat resistance.
  • Comparative Example 13 is a polycarbonate copolymer obtained by copolymerizing 1,1'-binaphthyl structure as a diol component BHEB with BPEF, but has a low refractive index.
  • Embodiment Example 21 of Embodiments [1] and [4] of the Present Invention 20.2 parts by weight of 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl (BCMB), 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl (BHEB) 72 parts by weight and 17.0 ⁇ 10 ⁇ 3 parts by weight of tetrabutoxytitanium were placed in a reactor equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere and normal pressure, and stirred for 20 minutes. Thereafter, the temperature was gradually raised and reduced, and finally the temperature was raised and reduced to 260 ° C.
  • BCMB 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl
  • BHEB 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all the monomer components (total dicarboxylic acid component + total diol component).
  • the specific viscosity of the obtained polyester resin was 0.28, the glass transition temperature Tg was 135 ° C., and the refractive index was 1.680.
  • Example 22 Polymerization was conducted in the same manner as in Example 21 except that BCMB was 20.12 parts by weight, BHEB was 14.98 parts by weight, and ethylene glycol (EG) was 6.83 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 40 mol% was derived from BHEB, and 10 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 132 ° C., and a refractive index of 1.679.
  • Example 23 Polymerization was conducted in the same manner as in Example 21 except that BCMB was 16.90 parts by weight, BHEB was 21.72 parts by weight, and diphenyl carbonate (DPC) was 3.64 parts by weight.
  • the obtained pellet was analyzed by NMR. As a result, the dicarboxylic acid component introduced into the polyester carbonate resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol introduced into the polyester carbonate resin.
  • the component was 58 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component).
  • the obtained polyester carbonate resin had a specific viscosity of 0.27, a glass transition temperature Tg of 132 ° C., and a refractive index of 1.678.
  • Example 24 Polymerization was conducted in the same manner as in Example 21, except that 22.93 parts by weight of 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl (BECMB) and 18.72 parts by weight of BHEB were used. The obtained pellets were analyzed by NMR.
  • the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester acid component + total diol component), and the diol component introduced into the polyester resin was all. It was 50 mol% with respect to the monomer component (total diester component + total diol component).
  • the specific viscosity of the obtained polyester resin was 0.28
  • the glass transition temperature Tg was 135 ° C.
  • the refractive index was 1.680.
  • Comparative Example 21 Polymerization was conducted in the same manner as in Example 21, except that BCMB was 20.12 parts by weight, BHEB was 11.23 parts by weight, and EG was 4.34 parts by weight.
  • the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 30 mol% was derived from BHEB, and 20 mol% was derived from EG.
  • the obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 128 ° C., and a refractive index of 1.777.
  • Comparative Example 22 Polymerization was conducted in the same manner as in Example 21 except that 9.71 parts by weight of dimethyl terephthalate (DMT), 18.72 parts by weight of BHEB, and 0 parts by weight of diphenyl carbonate (DPC) were used. The obtained pellets were analyzed by NMR. As a result, the diester acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester acid component + total diol component), and the diol component introduced into the polyester resin. It was 50 mol% with respect to all the monomer components (total diester acid component + total diol component).
  • DMT dimethyl terephthalate
  • BHEB BHEB
  • DPC diphenyl carbonate
  • the obtained polyester resin had a specific viscosity of 0.25, a glass transition temperature Tg of 127 ° C., and a refractive index of 1.658.
  • Comparative Example 23 Polymerization was conducted in the same manner as in Example 21 except for 21,93 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), 18.72 parts by weight of BHEB, and 21.85 parts by weight of DPC.
  • BPEF 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
  • the polycarbonate resin obtained had a specific viscosity of 0.23, a glass transition temperature Tg of 135 ° C., and a refractive index of 1.649.
  • Comparative Example 24 Polymerization was conducted in the same manner as in Example 21 except that 43.85 parts by weight of BPEF and 21.85 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, 100 mol% of the diol component introduced into the polycarbonate resin was derived from BPEF.
  • the polycarbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 147 ° C., and a refractive index of 1.638.
  • Example 21 Polymerization was carried out in the same manner as in Example 21 except that BCMB was 16.90 parts by weight, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene BPEF was 25.43 parts by weight, and DPC was 3.64 parts by weight.
  • the dicarboxylic acid component introduced into the polyester carbonate resin was introduced into the polyester carbonate resin in an amount of 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component).
  • the diol component was 58 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component).
  • the polyester carbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 150 ° C., and a refractive index of 1.660.
  • the value of Formula (2) in Table 3 is the ratio of the repeating unit represented by Formula (2) when the total of all repeating units is 100 mol%.
  • the polyesters or polyester carbonate resins obtained in Examples 21 to 23 in Table 3 are resins having a high refractive index, low birefringence, and a good balance between heat resistance and moldability, and are excellent as optical lenses.
  • the polymer of Comparative Example 21 has low heat resistance, and Comparative Example 22 does not sufficiently cancel out birefringence and has low heat resistance.
  • the birefringence obtained from the polymer is large and the heat resistance is poor.
  • Comparative Example 23 is a polycarbonate copolymer obtained by copolymerizing 1,1'-binaphthalene structure as a diol component BHEB with BPEF, but has a low refractive index.
  • thermoplastic resin of the present invention has a high refractive index, a low birefringence, and a high heat resistance, so an optical disk, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a substrate, It can be used for optical members such as optical filters and hard coat films, and is particularly useful for lenses.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Le premier but de la présente invention concerne une résine thermoplastique qui présente un indice de réfraction élevé, une faible biréfringence et une résistance élevée à la chaleur, en particulier une résine thermoplastique qui présente d'excellentes caractéristiques optiques. La solution de l'invention porte sur 1. une résine thermoplastique qui contient 70 % en mole ou plus de motifs récurrents représentés par la formule générale (1) ou la formule générale (2) dans tous les motifs. (Dans la formule (1), chaque radical parmi R1 et R2 représente, indépendamment, un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-10 atomes de carbone; chaque indice parmi n et m représente, indépendamment, un entier de 0 ou plus; chaque radical parmi R3-R10 représente, indépendamment, un atome d'hydrogène, un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode ou un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-12 atomes de carbone; chaque radical parmi R11 et R12 représente, indépendamment, un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-10 atomes de carbone; chaque indice parmi o et p représente, indépendamment; un entier de 0 ou plus; et chaque radical parmi R13 et R14 représente, indépendamment, un atome d'hydrogène ou un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-20 atomes de carbone.) (Dans la formule (2), chacun radical parmi R1 et R2 représente, indépendamment, un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-10 atomes de carbone; chacun indice parmi n et m représente, indépendamment, un entier de 0 ou plus; chaque radical parmi R3-R10 représente, indépendamment, un atome d'hydrogène, un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode ou un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1 à 12 atomes de carbone; chaque radical parmi R15 et R16 représente, indépendamment, un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-10 atomes de carbone; chaque indice parmi o et p représente, indépendamment, un entier de 0 ou plus; et chaque radical parmi R17-R24 représente, indépendamment, un atome d'hydrogène, un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode ou un groupe hydrocarboné qui peut contenir un groupe aromatique comprenant 1-12 atomes de carbone.)
PCT/JP2017/023665 2016-07-04 2017-06-28 Résine thermoplastique WO2018008483A1 (fr)

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US11261294B2 (en) 2017-08-30 2022-03-01 Teijin Limited Thermoplastic resin and optical member
JP2022166115A (ja) * 2018-03-12 2022-11-01 帝人株式会社 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、および該樹脂を用いた光学部材
CN111655754B (zh) * 2018-03-12 2022-08-19 帝人株式会社 聚酯树脂或聚酯碳酸酯树脂和使用该树脂的光学部件
JPWO2019176874A1 (ja) * 2018-03-12 2020-12-03 帝人株式会社 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、および該樹脂を用いた光学部材
EP3766913A4 (fr) * 2018-03-12 2021-04-07 Teijin Limited Résine polyester ou résine carbonate de polyester, et élément optique utilisant ladite résine
KR20200088490A (ko) * 2018-03-12 2020-07-22 데이진 가부시키가이샤 폴리에스테르 수지 또는 폴리에스테르카보네이트 수지, 및 그 수지를 사용한 광학 부재
TWI823908B (zh) * 2018-03-12 2023-12-01 日商帝人股份有限公司 聚酯樹脂或聚酯碳酸酯樹脂及使用該樹脂之光學構件
KR102415803B1 (ko) 2018-03-12 2022-06-30 데이진 가부시키가이샤 폴리에스테르 수지 또는 폴리에스테르카보네이트 수지, 및 그 수지를 사용한 광학 부재
CN111655754A (zh) * 2018-03-12 2020-09-11 帝人株式会社 聚酯树脂或聚酯碳酸酯树脂和使用该树脂的光学部件
WO2019176874A1 (fr) * 2018-03-12 2019-09-19 帝人株式会社 Résine polyester ou résine carbonate de polyester, et élément optique utilisant ladite résine
JP7204735B2 (ja) 2018-03-12 2023-01-16 帝人株式会社 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、および該樹脂を用いた光学部材
US11566102B2 (en) 2018-03-12 2023-01-31 Teijin Limited Polyester resin or polyester carbonate resin, and optical member using said resin
US11578168B2 (en) 2018-03-30 2023-02-14 Teijin Limited Polycarbonate resin and optical member containing same
WO2022091780A1 (fr) * 2020-10-27 2022-05-05 帝人株式会社 Résine thermoplastique et élément optique comprenant celle-ci
WO2023210833A1 (fr) * 2022-04-26 2023-11-02 Mitsubishi Gas Chemical Company, Inc. Composés de binaphtyle oligomériques et résines thermoplastiques

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