Classifications

• • 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
• • 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
  • C08G63/02—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
• • 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
  • 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
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • 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
• • 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 and an optical lens containing the same. More specifically, the present invention relates to polyester carbonate resins or polyester resins, and optical lenses containing the same.
• Optical glass or optical resin is used as a material for optical lenses used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras.
• Optical glass has excellent 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.
• Patent Documents 1 to 5 When using optical resin as an optical lens, in addition to optical properties such as refractive index and Abbe number, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and heat and humidity resistance are required. Particularly in recent years, there has been a demand for optical lenses with high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 5).
• An object of the present invention is to provide a thermoplastic resin that has excellent optical properties such as refractive index and Abbe number, and is also excellent in heat resistance, and an optical lens using the same.
• the present inventors have discovered that the refractive index can be improved by using biphenanthrols as raw materials and monomers having a specific structure derived from dicarboxylic acid compounds. It was discovered that a thermoplastic resin having excellent optical properties such as Abbe's number and excellent heat resistance can be obtained, and the present invention was completed.
• thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) (In the formula, R 1 each independently represents an alkylene group having 1 to 4 carbon atoms, and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a group or a halogen atom, n each independently represents 0 or an integer of 1 to 4, and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom having 2 to 4 carbon atoms.
• R 1 each independently represents an alkylene group having 1 to 4 carbon atoms
• R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a group or a halogen atom
• n each independently represents 0 or an integer of 1 to 4
• R 3 each independently represents a hydrogen atom, an alkyl
• thermoplastic resin according to ⁇ 1> above wherein the monomer represented by the general formula (1) is a monomer represented by the following general formula (1a-1).
• R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1)).
• the thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (6) and/or a structural unit (C) derived from a monomer represented by the following general formula (7).
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 3> above.
• R a and R b each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted alkoxyl group having 1 to 20 carbon atoms.
• a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent
• a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent
• R h is an aryl group having 6 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent and contains one or more heterocyclic atoms selected from O, N and S.
• X is a single bond or represents a fluorene group which may have a substituent
• a and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent
• m and n each independently represent an integer from 0 to 6
• a and b each independently represent an integer from 0 to 10.
• R c and R d each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxyl group having 1 to 20 carbon atoms which may have a substituent.
• a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent
• Y 1 is a single bond, a fluorene group which may have a substituent, or a structural formula represented by the following formulas (8) to (14), (In formulas (8) to (14), R 61 , R 62 , R 71 and R 72 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent A carbon atom having 1 to 20 carbon atoms and optionally having a substituent, which represents an aryl group having 6 to 30 carbon atoms, or is formed by combining R 61 and R 62 or R
• thermoplastic resin represents a ring or heterocycle, r and s each independently represent an integer from 0 to 5000.
• a and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, p and q each independently represent an integer from 0 to 4, a and b each independently represent an integer from 0 to 10.
• ⁇ 5> The thermoplastic resin according to ⁇ 4> above, wherein in the general formula (6) and general formula (7), A and B each independently represent an alkylene group having 2 or 3 carbon atoms. .
• thermoplastic resin according to ⁇ 4> or ⁇ 5> above wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA.
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 6> above including a structural unit (D) derived from a monomer represented by the following general formula (5).
• L 1 each independently represents a divalent linking group
• R 3 and R 4 each independently represent a halogen atom or a substituent having 1 to 20 carbon atoms which may contain an aromatic group
• j3 and j4 each independently represent an integer from 0 to 4
• t represents an integer of 0 or 1.
• R 3 and R 4 in the general formula (5) each independently represent a methyl group, phenyl group, or naphthyl group
• L 1 in the general formula (5) each independently represents a substituent.
• the thermoplastic resin according to ⁇ 7> above which represents an optional alkylene group having 1 to 5 carbon atoms.
• the monomer represented by the general formula (5) is the thermoplastic resin described in ⁇ 7> or ⁇ 8> above, which has a structure represented by the following formula (5').
• R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group
• R 3 and R 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a carbon number 2 ⁇ 5 alkylene glycol
• Mw polystyrene equivalent weight average molecular weight
• nD refractive index
• thermoplastic resin that has excellent optical properties such as refractive index and Abbe's number, and is also excellent in heat resistance, and an optical lens containing the same.
• Crystal I Difference between crystal I and (crystal ⁇ ) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-2)) obtained in Synthesis Example 1 It is a figure which shows the chart of scanning calorimetry. Crystal ⁇ (crystal I) of 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)) obtained in Synthesis Example 1, It is a figure which shows the chart of powder X-ray diffraction (PXRD) measurement.
• PXRD powder X-ray diffraction
• thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1).
• the biphenanthrene compound used in the present invention is represented by the following general formula (1).
• R 1 each independently represents an alkylene group having 1 to 4 carbon atoms
• R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms. or represents a halogen atom
• n each independently represents 0 or an integer of 1 to 4
• R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 2 to 4 carbon atoms.
• the alkali metal salt of the biphenanthrene compound used in the present invention is represented by the following general formula (1').
• M each independently represents an alkali metal atom
• R 1 , R 2 and n have the same definition as in general formula (1).
• R 1 in general formulas (1) and (1') each independently represents an alkylene group having 1 to 4 carbon atoms, and this alkylene group may be either linear or branched. Specific examples include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, and 1,4-butylene group.
• R 1 in general formulas (1) and (1') is preferably an alkylene group each independently having 1 or 2 carbon atoms, and a methylene group, a 1,1-ethylene group or a 1,2-ethylene group is preferable. More preferred are methylene groups or 1,2-ethylene groups, and particularly preferred are methylene groups.
• R 2 in the general formulas (1) and (1') each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. Among these, an aryl group having 6 to 18 carbon atoms or a halogen atom is preferred.
• R 2 is an alkyl group, in addition to linear or branched alkyl groups, cyclic alkyl groups having 5 to 6 carbon atoms are included, and among these, each group independently has 1 to 4 carbon atoms. Alkyl groups are preferred, alkyl groups each independently having 1 or 2 carbon atoms are more preferred, and methyl groups are particularly preferred.
• R 2 is an aryl group, it is preferably an aryl group each independently having 6 to 12 carbon atoms, more preferably each independently having 6 to 8 carbon atoms, and particularly preferably a phenyl group.
• R 2 is a halogen atom
• examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
• n each independently represents 0 or an integer of 1 to 4. Among these, each independently is preferably 0, 1, or 2, each independently more preferably 0 or 1, and particularly preferably 0.
• R 3 in the general formula (1) each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms.
• R 3 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is preferable from the viewpoint of solvent solubility that R 3 is an alkyl group having 1 to 6 carbon atoms.
• R 3 is an alkyl group having 1 to 6 carbon atoms, it includes linear or branched alkyl groups as well as cyclic alkyl groups having 5 to 6 carbon atoms.
• Alkyl groups having 1 to 4 carbon atoms are preferred, alkyl groups each independently having 1 or 2 carbon atoms are more preferred, and ethyl groups are particularly preferred.
• R 3 is an alkenyl group having 2 to 4 carbon atoms, each independently is preferably an alkenyl group having 2 or 3 carbon atoms, and each independently is more preferably a vinyl group or an allyl group.
• allyl group is particularly preferable.
• M in general formula (1') each independently represents an alkali metal atom.
• M is each independently preferably lithium, sodium, or potassium, each independently more preferably sodium or potassium, and even more preferably potassium.
• the biphenanthrene compound used in the present invention is a 9,9'-biphenanthrene compound with the general formula ( 1a).
• R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).
• the general formula (1a ) is preferred.
• R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).
• biphenanthrene compounds represented by the general formula (1a-1) preferred compounds are shown below.
• Examples of the biphenanthrene compound represented by the general formula (1b) include the compound groups (1b-1) to (1b-4). (1b-1) 1,1'-biphenanthrene compound (1b-2) 2,2'-biphenanthrene compound
• the biphenanthrene compound used in the present invention represented by general formula (1) is preferably a biphenanthrene compound represented by formula (1a), and more preferably a biphenanthrene compound represented by formula (1a-1). .
• crystals of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1) are solids having crystallinity. It is very useful because it can be handled as In powder X-ray diffraction peak patterns using Cu-K ⁇ rays, such crystals have diffraction angles 2 ⁇ of 9.9 ⁇ 0.2°, 13.8 ⁇ 0.2°, 20.0 ⁇ 0.2°, and 20.7. It has characteristic diffraction peaks at ⁇ 0.2°, 22.0 ⁇ 0.2° and 22.4 ⁇ 0.2°.
• crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2), have crystallinity. It is very useful because it can be handled as a solid and has excellent handling properties, and has low hygroscopicity and excellent storage stability.
• crystal ⁇ In the diffraction peak pattern, characteristic diffraction peaks at diffraction angles 2 ⁇ of 10.8 ⁇ 0.2°, 17.5 ⁇ 0.2°, 21.7 ⁇ 0.2° and 23.0 ⁇ 0.2° There are crystals with This crystal further has diffraction peaks at diffraction angles 2 ⁇ of 12.3 ⁇ 0.2°, 15.0 ⁇ 0.2°, 20.0 ⁇ 0.2° and 20.8 ⁇ 0.2°. is preferred. It is preferable that these diffraction peaks have a relative integrated intensity of 10 or more based on the peak with the highest integrated intensity. Since the integrated intensity may vary, the crystalline phase can be identified based on the analysis method of normal powder X-ray diffraction analysis. Hereinafter, such a crystal may be referred to as "crystal ⁇ ".
• the onset temperature of the endothermic peak of this crystal ⁇ by differential scanning calorimetry is preferably in the range of 153 to 162°C, more preferably in the range of 154 to 160°C, and more preferably in the range of 155 to 159°C. This is particularly preferred.
• the onset temperature of the endothermic peak measured by differential scanning calorimetry (DSC) is sometimes referred to as the melting point.
• ⁇ Crystal I of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile Another aspect of the crystal of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), is that the endothermic peak is determined by differential scanning calorimetry.
• such a crystal may be referred to as "crystal I”.
• the onset temperature of an endothermic peak determined by differential scanning calorimetry (DSC) may be referred to as a melting point.
• crystals that have This crystal preferably has peaks at diffraction angles 2 ⁇ of 6.0 ⁇ 0.2° and 11.9 ⁇ 0.2°, and further has peaks at diffraction angles 2 ⁇ of 9.7 ⁇ 0.2° and 19. It is more preferable to have peaks at 7 ⁇ 0.2° and 22.4 ⁇ 0.2°. It is preferable that these diffraction peaks have a relative integrated intensity of 10 or more based on the peak with the highest integrated intensity. Since the integrated intensity may vary, the crystalline phase can be identified based on the analysis method of normal powder X-ray diffraction analysis. Hereinafter, such a crystal may be referred to as "crystal ⁇ ".
• the onset temperature of the endothermic peak determined by differential scanning calorimetry is preferably in the range of 160 to 170°C, more preferably in the range of 164 to 170°C, and more preferably in the range of 165 to 170°C. This is particularly preferred.
• the onset temperature of an endothermic peak measured by differential scanning calorimetry (DSC) is sometimes referred to as the melting point.
• Crystals (crystal ⁇ , crystal I, crystal ⁇ and crystal II) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), are:
• the purity by high performance liquid chromatography is preferably 95.0% or more, more preferably 98.0% or more, even more preferably 98.5% or more, and 99.0% or more. It is particularly preferable.
• Crystals (crystal ⁇ , crystal I, crystal ⁇ and crystal II) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), are:
• the hue measured in a tetrahydrofuran solution with a concentration of 10% by weight of the crystal is preferably APHA 250 or less, more preferably APHA 150 or less, even more preferably APHA 100 or less, and APHA 50 or less. Particularly preferred.
• crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
• crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
• Such crystals have diffraction angles 2 ⁇ of 5.4 ⁇ 0.2°, 10.4 ⁇ 0.2°, 13.4 ⁇ 0.2°, and 17.4 in powder X-ray diffraction peak patterns using Cu-K ⁇ rays. It has characteristic diffraction peaks at ⁇ 0.2°, 20.0 ⁇ 0.2° and 22.0 ⁇ 0.2°.
• biphenanthrene compound (monomer) represented by general formula (1) in the present invention there are no particular limitations on the starting materials and manufacturing method for its production.
• the biphenanthrene compound represented by the general formula (1) it is preferable to use biphenanthrols represented by the general formula (2) as raw materials, and among them, the biphenanthrene compound represented by the general formula (2a) is preferably used as a raw material. More preferably, they are rolls, and even more preferably biphenanthrols represented by the general formula (2a-1).
• R 2 and n have the same definition as in general formula (1).
• R 2 and n have the same definition as in general formula (1).
• R 2 and n have the same definition as in general formula (1).
• the method for producing the biphenanthrene compound represented by the general formula (1) includes, for example, biphenanthrols represented by the general formula (2) and halogenated carboxylic acids represented by the general formula (3).
• Examples include a method of obtaining a compound represented by general formula (1) by an etherification reaction in which the following compounds are reacted under alkaline conditions.
• the target compound, a compound represented by general formula (1) is produced by an etherification reaction of one molecule of a halogenated carboxylic acid represented by general formula (3) with a biphenanthrol represented by general formula (2).
• the monoetherified product is produced as an intermediate, and the monoetherified product undergoes an etherification reaction with another molecule of halogenated carboxylic acid represented by the general formula (3).
• a method for obtaining a compound represented by general formula (1'), that is, an alkali metal salt, by alkaline hydrolysis or neutralization of the compound represented by general formula (1) with an alkali metal hydroxide is mentioned.
• a compound represented by general formula (1') By protonating a compound represented by general formula (1') using an acid, a compound represented by general formula (1'), which corresponds to the case where R 3 in general formula (1) is a hydrogen atom, is obtained. Examples include methods for obtaining dicarboxylic acid compounds.
• R 1 , R 2 , n, and R 4 have the same definitions as in general formula (1), and M has the same definition as in general formula (1'), X represents a halogen atom, and MOH represents an alkali metal hydroxide. means.
• 9,9'-biphenanthrene-10,10'-diol which is a biphenanthrole represented by the general formula (2), and ethyl chloroacetate, which is a halogenated carboxylic acid represented by the general formula (3).
• the reaction formula of the etherification reaction is shown to obtain a compound represented by formula (1a-1-2), which is a biphenanthrene compound represented by general formula (1).
• a potassium salt among alkali metal salts is obtained by using a compound represented by formula (1a-1-2) as a compound represented by general formula (1) and potassium hydroxide as an alkali metal hydroxide.
• the reaction formula is shown below.
• the obtained potassium salt is converted into a dicarboxylic acid compound represented by the general formula (1') corresponding to the case where R 3 is a hydrogen atom in the general formula (1).
• the reaction formula for obtaining -1) is shown below.
• Biphenanthrols In the production of the biphenanthrene compound represented by general formula (1) used in the present invention, biphenanthrols represented by general formula (2) are used. In the formula, R 2 and n have the same definition as in general formula (1). Biphenanthrols represented by general formula (2) can be produced, for example, by the production method described in JP-A No. 2001-039898.
• the biphenanthrene skeleton-containing dihydroxy compound represented by the general formula (1a-1) used in the present invention can be produced using a biphenanthrole represented by the general formula (2a-1) as a raw material. In the formula, R 2 and n have the same definition as in general formula (1).
• Examples of the biphenanthrols represented by the general formula (2a-1) include 10,10'-dihydroxy-9,9'-biphenanthrile (CAS registration number: 110071-78-8). This compound can be produced, for example, by the method described in JP-A-60-181043, Journal of American Chemical Society, 2008, 130, 6840, and the like. In addition, 10,10'-dihydroxy-6,6'-diphenyl-9,9'-biphenanthryl (CAS registration number: 1564249-14-4), 10,10'-dihydroxy-6,6'-dibromo-9, 9'-biphenanthrile (CAS registration number: 1564249-12-2) is mentioned, and these compounds are described in Tetrahedron, 70, 1786-1793 (2014).
• the biphenanthrene skeleton-containing dihydroxy compound represented by the general formula (1b) used in the present invention can be produced using a biphenanthrole represented by the general formula (2b) as a raw material.
• Examples of the biphenanthrols represented by the general formula (2b) include the following compounds. Mention may be made of 2,2'-dihydroxy-1,1'-biphenanthryl (CAS Registration Number: 196865-17-5), which compound is described in Chinese Patent Application No. 103787837. 1,1'-dihydroxy-3,3'-diphenyl-2,2'-biphenanthryl (CAS registration number: 1624364-17-5), and these compounds are described in Catalysis Science & Technology, 4, 4406-4415 (2014). It is described in.
• Examples include 1,1'-dihydroxy-2,2'-biphenanthryl, 1,1'-dihydroxy-3,3'-biphenanthryl, and 2,2'-dihydroxy-3,3'-biphenanthryl.
• 2,2'-dihydroxy-4,4'-diphenyl-3,3'-biphenanthryl (CAS registration number: 1793116-18-3) is mentioned, and this compound is described in Chemical Communications (Cambridge, United Kingdom), 51, 10498-10501 (2015).
• Mention may be made of 4,4'-dihydroxy-3,3'-biphenanthryl (CAS Registration Number: 2376151-04-9), which compound is described in Chinese Patent Application No. 109336887.
• halogenated carboxylic acids represented by the general formula (3) to be reacted with biphenanthrols
• Halogenated alkyl acetate such as isobutyl acetate, tert-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, tert-butyl bromoacetate
• chloro Halogenated alkenyl acetate such as vinyl acetate, allyl chloroacetate, vinyl bromoacetate, allyl bromoacetate
• halogenated alkyl acetate or halogenated alkenyl acetate is preferable, methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, vinyl chloroacetate, allyl chloroacetate are more preferable, and methyl chloroacetate, ethyl chloroacetate, bromoethyl acetate are more preferable. Methyl acetate and ethyl bromoacetate are more preferred, and methyl chloroacetate and ethyl chloroacetate are particularly preferred.
• the molar ratio of halogenated carboxylic acids to biphenanthrols is not particularly limited as long as it is at least the theoretical value (2.0), but it is usually in the range of 2 to 20 times the molar amount, preferably 2 to 20 times the molar amount. It is used in a range of 10 times the molar amount, more preferably in a range of 2 to 6 times the molar amount.
• the reaction is carried out in the presence of a base, and examples of the base used include triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
• the molar ratio of the base to be charged is usually 0.8 to 4 times the molar amount, preferably 0.85 to 3 times the molar amount, more preferably 0.9 to 2 times the molar amount of the halogenated carboxylic acid. range of amounts.
• catalysts may be used, such as alkali metal bromide salts such as sodium bromide and potassium bromide, alkali metal iodide salts such as sodium iodide and potassium iodide, ammonium bromide and ammonium iodide, etc. can be mentioned.
• the amount of the catalyst used is usually in the range of 0.1 to 100% by weight, preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 0.1 to 10% by weight, based on the biphenanthrols. be.
• the reaction temperature is usually in the range of 25 to 120°C, preferably in the range of 40 to 100°C, more preferably in the range of 50 to 90°C, particularly preferably in the range of 60 to 80°C. If the reaction temperature is high, the yield will decrease, and if the reaction temperature is low, the reaction rate will be slow, which is not preferable.
• reaction pressure there is no restriction on the reaction pressure, and the reaction may be carried out under normal pressure, reduced pressure, or increased pressure. Normal pressure or reduced pressure is preferred.
• the reaction under pressure the reaction can be carried out in a pressurized state in which, for example, a gas inert to the reaction, such as nitrogen, is passed. By doing so, the carbon dioxide gas generated from the carbonate or hydrogen carbonate used in the reaction can be discharged out of the reaction system, thereby promoting the reaction. From the viewpoint of shortening the reaction time, it is more preferable to perform the reaction under reduced pressure.
• the reaction under reduced pressure By conducting the reaction under reduced pressure, the carbon dioxide gas generated from the carbonate or hydrogen carbonate used in the reaction can be discharged out of the reaction system, so the reaction is accelerated and is faster than the reaction under normal pressure.
• the reaction pressure is preferably in a range of 5 kPa or more and 80 kPa or less, more preferably 10 kPa or more and 80 kPa or less, and even more preferably 30 kPa or more and 60 kPa or less.
• the reaction pressure can be reduced by a pressure reducing device, and if the reaction pressure is maintained within the above range, the pressure reducing device may be operated intermittently or continuously, but it cannot be operated continuously. More preferred.
• the reaction solvent is not particularly limited as long as it cannot be distilled out from the reaction vessel at the reaction temperature and is inert to the reaction, but examples include acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran, and 1,4- Ethers such as dioxane, 1,3-dioxane, diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, etc.
• organic solvents may be used alone or in combination of two or more to adjust polarity.
• ketone solvents having 3 to 9 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, or acetonitrile, dimethyl sulfoxide, dimethyl formamide, N-methyl pyrrolidone, etc.
• Aprotic polar solvents are preferred, ketone solvents having 3 to 8 carbon atoms or acetonitrile are more preferred, ketone solvents having 3 to 6 carbon atoms or acetonitrile are even more preferred, and methyl isobutyl ketone is particularly preferred.
• methyl isobutyl ketone is used as a reaction solvent, it is also preferable because water washing can be performed to remove water-soluble impurities such as salts.
• the amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually preferably used in a range of 1 to 7 times the weight of the biphenanthrols, more preferably 2 to 4 times the weight of the biphenanthrols.
• the amount of solvent to be used is preferably 1.5 to 10 times the weight of the biphenanthrols; It is more preferable to use the amount in a range of 8 times by weight, and even more preferably in a range of 2 to 6 times by weight.
• the amount of distillation per hour during the reaction by distilling the solvent out of the reaction system is preferably in the range of 0.05 to 1.5 times the weight of the biphenanthrols, and 0.05 to 1.5 times the weight of the biphenanthrols.
• the range of 1 to 1.0 times by weight is more preferable, the range of 0.3 to 1.0 times by weight is even more preferable, and the range of 0.3 to 0.8 times by weight is particularly preferable.
• the amount of distillation per hour may vary within the above range, or the amount of distillation may temporarily exceed the upper or lower limit of the above range.
• the end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is hardly seen at the time when unreacted biphenanthrols disappear and no increase in the target product is observed, or after unreacted biphenanthrols disappear and a monoetherified product, which is a reaction intermediate, is generated. It is preferable that the end point of the reaction is the point at which the amount disappears. Regarding the point at which the monoetherified product, which is a reaction intermediate, is almost no longer seen after being produced, specifically, the point at which it becomes 1.5 area% or less in the above analysis of the monoetherified product, more preferably 1.0 area. % or less, more preferably 0.8 area % or less, particularly preferably 0.5 area % or less.
• the reaction time varies depending on the reaction conditions such as reaction temperature, but it is usually completed in about 1 to 30 hours.
• the water content of the reaction solution in the etherification reaction is preferably in the range of 0.01% by weight or more and 2.0% by weight or less based on the biphenanthrols. be.
• the amount of water in the reaction solution within the above range the biphenanthrene compound of the present invention can be produced with a good reaction yield.
• the upper limit of this moisture content is more preferably 1.5% by weight or less, even more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less.
• methods for controlling the water content of the reaction solution within this range include a method of using previously dehydrated raw materials and solvents, and a method of distilling and removing water before the etherification reaction.
• the biphenanthrene compound represented by general formula (1) is an ester compound
• the etherification reaction neutralization, water washing, crystallization, filtration, distillation, column chromatography, etc.
• Purification and isolation can be achieved by performing post-processing operations such as separation.
• purification by distillation, recrystallization, or column chromatography may be performed according to conventional methods.
• the reaction product mixture is preferably neutralized and washed with water, and then a crystallization operation is performed.
• crystal I and crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2)
• the manufacturing method is selected from 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and a ketone solvent having 3 to 9 carbon atoms.
• aromatic hydrocarbon solvent having 6 to 9 carbon atoms include benzene, toluene, xylene, and mesitylene, and aromatic hydrocarbon solvents having 7 to 9 carbon atoms are preferable. 7 or 8 aromatic hydrocarbon solvents are more preferred, and toluene is particularly preferred.
• ketone solvents having 3 to 9 carbon atoms include linear ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isoamyl ketone, and cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, and isophorone. Examples include ketone solvents. Among these, chain ketone solvents having 3 to 9 carbon atoms are preferred, chain ketone solvents having 3 to 6 carbon atoms are more preferred, and acetone or methyl isobutyl ketone is particularly preferred.
• the amount of the organic solvent used can be adjusted as appropriate in consideration of the solubility depending on the type of organic solvent used, but the amount of the compound represented by formula (1a-1-2) is 0. .5 to 10 times by weight, more preferably 1 to 8 times by weight, even more preferably 1 to 6 times by weight, and even more preferably 1.5 to 4 times by weight. Particularly preferred.
• the temperature at which the compound represented by formula (1a-1-2) is dissolved in an organic solvent to form a solution can be adjusted as appropriate in consideration of the type of organic solvent used, but is within the range of 40 to 90°C. It is.
• Examples of the poor solvent used when crystals are precipitated by mixing a poor solvent include water, an alcohol solvent having 1 to 4 carbon atoms, and an aliphatic hydrocarbon solvent having 5 to 8 carbon atoms.
• the poor solvent to be mixed is at least one selected from these, and it is preferable to select one from among these.
• Specific examples of alcohol solvents having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc. Alcohol solvents having 1 to 3 carbon atoms are preferred; Alcohol solvents having 1 or 2 carbon atoms are more preferred, and methanol is particularly preferred.
• Examples of the aliphatic hydrocarbon solvent having 5 to 8 carbon atoms include, for example, chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms such as pentane, hexane, heptane, octane, and isooctane, and cyclopentane.
• Examples include cyclic aliphatic hydrocarbon solvents having 5 to 8 carbon atoms such as cyclohexane, cycloheptane, and the like.
• chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms are preferred, chain aliphatic hydrocarbon solvents having 6 to 8 carbon atoms are more preferred, and chain aliphatic hydrocarbon solvents having 7 carbon atoms are preferred.
• Hydrocarbon solvents are more preferred, with normal heptane being particularly preferred.
• the amount of the poor solvent used should be adjusted as appropriate, taking into account the amount of solution of the compound represented by formula (1a-1-2), the type of organic solvent, and the solubility depending on the type of poor solvent used. However, it is in a range of 0.5 to 10 times by weight, more preferably in a range of 1 to 8 times by weight, relative to the amount of the compound represented by formula (1a-1-2). A range of 1 to 6 times by weight is more preferable, and a range of 1.5 to 4 times by weight is particularly preferable.
• the temperature at which crystals of the compound represented by formula (1a-1-2) are precipitated by the operation of mixing a poor solvent is not particularly limited, but is in the range of 20 to 85°C.
• the poor solvent used when crystals are precipitated by the operation of mixing the poor solvents described above may be mixed.
• the temperature at which the solution of the compound represented by formula (1a-1-2) is cooled to precipitate crystals is from the temperature at which it is dissolved to form a solution, and is not particularly limited; It is in the range of 80°C.
• seed crystals do not need to be used when crystals are precipitated, it is preferable to use seed crystals.
• crystal II and crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2)
• a method for producing it is to heat crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile to a temperature of 150° C. or more and 165° C. or less to melt it, and then cool it.
• the crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile used are preferably Crystal I and Crystal ⁇ .
• the purity by high performance liquid chromatography is preferably 95.0% or more, more preferably 98.0% or more, even more preferably 98.5% or more, and 99.0% or more. This is particularly preferred.
• the temperature range during heating is preferably 150°C or more and 163°C or less, more preferably 150°C or more and 160°C or less.
• the cooling temperature is not particularly limited as long as it crystallizes and becomes solid, and may be cooled to room temperature. When melting by heating, it is preferable that the 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile crystals do not remain unmelted.
• the alkali metal salt of the biphenanthrene compound represented by the general formula (1') can be prepared by performing post-reaction treatments such as neutralization and water washing after the completion of the etherification reaction, and purifying the obtained ester compound.
• the alkali metal salt of the biphenanthrene compound represented by the general formula (1') can be obtained by subjecting the crude product to alkaline hydrolysis.
• the alkaline compound used in alkaline hydrolysis is not particularly limited, but preferably is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and is usually prepared as an aqueous solution with a concentration of 12 to 60% by weight. used.
• such an alkali compound is usually used in an amount of 2 mol or more, preferably in the range of 2.1 to 10 mol, per 1 mol of the ester compound of the biphenanthrene compound represented by the general formula (1).
• water is used as a reaction solvent in the hydrolysis reaction, but if necessary, organic solvents such as alcohols and ketones that are miscible with water in any proportion, or mixtures of such organic solvents and water may be used. Solvents are also used. It is also possible to continue to use the reaction solvent used in the etherification reaction, such as methyl isobutyl ketone or acetonitrile.
• the reaction temperature for hydrolysis is usually in the range of 30 to 100°C, preferably in the range of 50 to 90°C, and under such reaction conditions, the reaction is usually completed in about 1 to 5 hours. .
• crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
• crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
• potassium hydroxide as the alkaline compound used in the hydrolysis and precipitating crystals of the potassium salt by the method described above.
• the ester compound obtained by the etherification reaction is subjected to alkaline hydration. It can be obtained by decomposing the reaction solution and making it acidic using a strong acid such as hydrochloric acid. This method is preferable in order to obtain a highly pure carboxylic acid compound. It can be purified and isolated by performing post-treatment operations such as neutralization, water washing, crystallization, filtration, distillation, and separation by column chromatography according to conventional methods.
• a suitable production method is one in which a carboxylic acid salt is once extracted from a reaction mixture obtained by alkali hydrolysis of an ester compound obtained by the reaction, and a carboxylic acid compound is obtained using this carboxylic acid salt and an acid.
• the crystals of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-1) are crystallized. It can be manufactured by performing post-processing operations.
• a solvent selected from 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and a ketone solvent having 3 to 9 carbon atoms.
• the solvent is preferably a ketone solvent having 3 to 9 carbon atoms, more preferably a chain ketone solvent having 3 to 9 carbon atoms, even more preferably a chain ketone solvent having 3 to 6 carbon atoms, and acetone. or methyl isobutyl ketone is particularly preferred.
• the operations for precipitating crystals include mixing a poor solvent in which the compound represented by formula (1a-1-1) has low solubility, cooling the solution, and removing the solvent of the solution by distillation. can do.
• Each process such as reaction, alkaline hydrolysis, neutralization, water washing, crystallization, filtration, distillation, separation by column chromatography, drying, packaging, etc., is carried out in order to suppress oxidation, deterioration, coloration, etc. due to the influence of oxygen. It is preferable to carry out under an inert gas atmosphere such as , nitrogen, or argon.
• thermoplastic resin in one embodiment of the present invention includes, but is not particularly limited to, polyester resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethacrylate resin, etc., but polyester carbonate resin or polyester resin is used. It is preferable that
• the ratio of the structural unit (A) represented by the above formula to all structural units is not particularly limited, but it is preferably 1 to 80 mol% of all structural units. , more preferably 1 to 60 mol%, particularly preferably 5 to 50 mol%.
• the thermoplastic resin of one embodiment of the present invention is derived from an aliphatic dihydroxy compound generally used as a structural unit of polycarbonate resin or polyester carbonate resin. It can include a structural unit derived from an aromatic dihydroxy compound or a structural unit derived from an aromatic dihydroxy compound.
• various aliphatic dihydroxy compounds can be mentioned, but in particular, ethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,3-adamantanedimethanol, 2,2 -bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-( 5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexane Examples include diol.
• aromatic dihydroxy compounds can be mentioned, but in particular, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, and 1,1-bis( 4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl) ) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ketone, bisphenoxyethanolfluorene, and the like.
• bisphenol A bis(4-hydroxyphenyl)methane
• 1,1-bis( 4-hydroxyphenyl)ethane 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane
• thermoplastic resin of one Embodiment of this invention contains the structural unit (B) derived from the monomer represented by the following general formula (6).
• R a and R b each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number 1 to 20 which may have a substituent.
• R h is an aryl group having 6 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituent and which contains one or more hetero ring atoms selected from O, N and S.
• R a and R b preferably include a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and one or more heterocyclic atoms selected from O, N, and S.
• a heteroaryl group having 6 to 20 carbon atoms which may have a group, more preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom. It is an aryl group having 6 to 12 carbon atoms which may have an atom or a substituent.
• X represents a single bond or a fluorene group which may have a substituent.
• X is preferably a single bond or a fluorene group having a total of 12 to 20 carbon atoms and which may have a substituent.
• a and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 2 or 3 carbon atoms.
• m and n are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.
• a and b are each independently an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.
• structural unit (B) examples include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.
• thermoplastic resin of one embodiment of the present invention has a structural unit (C) derived from a monomer represented by the following general formula (7).
• R c and R d each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number 1 to 20 which may have a substituent.
• R c and R d preferably contain a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and one or more heterocyclic atoms selected from O, N, and S.
• a heteroaryl group having 6 to 20 carbon atoms which may have a group, more preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom. It is an aryl group having 6 to 12 carbon atoms which may have an atom or a substituent.
• Y 1 is a single bond, a fluorene group which may have a substituent, or a structural formula represented by the following formulas (8) to (14), and is preferably , a single bond, or a structural formula represented by the following formula (8).
• R 61 , R 62 , R 71 and R 72 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. , or represents an aryl group having 6 to 30 carbon atoms which may have a substituent, or has a substituent formed by R 61 and R 62 or R 71 and R 72 bonding to each other. represents a carbon ring or heterocycle having 1 to 20 carbon atoms.
• r and s are each independently an integer of 0 to 5000.
• a and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 2 or 3 carbon atoms.
• p and q are each independently an integer of 0 to 4, preferably 0 or 1.
• a and b are each independently an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, for example, 0 or 1.
• structural unit (C) examples include BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF(9,9-bis(4-(2-hydroxyethoxy)-3- (phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol (4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1- phenylethylidene) bisphenol), bisphenol P-CDE (4,4'-cyclododecylidene bisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylid)
• the thermoplastic resin of one embodiment of the present invention includes a polymer that includes the structural unit (A) as an essential component, but contains the structural unit (B) and does not contain the structural unit (C), and a polymer that contains the structural unit (C) and does not contain the structural unit (C).
• a polymer that includes the structural unit (A) as an essential component but contains the structural unit (B) and does not contain the structural unit (C)
• a polymer that contains the structural unit (C) and does not contain the structural unit (C) In addition to polymers that do not contain B), copolymers having the structural unit (B) and the structural unit (C), mixtures of polymers having the structural unit (B) and polymers having the structural unit (C), A combination of these may also be used.
• Examples of polymers containing the structural unit (C) but not the structural unit (B) include those having the structural units of the following formulas (I-1) to (I-3), in which the structural unit (B) and Examples of the copolymer having the structural unit (C) include those having the structural units of the following formulas (II-1) to (II-4).
• m and n are each an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1
• the number of repeating units of formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.
• both block copolymers and random copolymers in which the values of m and n are large, for example, 100 or more can be employed, but random copolymers are preferable. More preferably, a random copolymer in which the values of m and n are 1 is used.
• m and n are each independently an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.
• polymers having multiple types of structural units both block copolymers and random copolymers in which the values of m and n (or m, n, and l) are large, for example, 100 or more, can be adopted.
• a random copolymer is preferred, and more preferably a random copolymer in which the values of m and n (or m, n, and l) are 1 is used.
• the molar ratio of the structural unit (B) and the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, and 15 :85 to 85:15 is more preferable, and 30:70 to 70:30 is particularly preferable.
• the mass ratio of the polymer having the structural unit (B) to the polymer having the structural unit (C) is preferably 1:99 to 99:1, and preferably 10:90 to 90:10. The ratio is more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.
• the thermoplastic resin of one Embodiment of this invention contains the structural unit (D) derived from the monomer represented by the following general formula (5).
• L 1 each independently represents a divalent linking group
• R 3 and R 4 each independently represent a halogen atom or a substituent having 1 to 20 carbon atoms which may contain an aromatic group
• j3 and j4 each independently represent an integer from 0 to 4
• t represents an integer of 0 or 1.
• R 3 and R 4 in the general formula (5) each independently represent a methyl group, a phenyl group, or a naphthyl group. It is preferable that L 1 in the general formula (5) each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent.
• the monomer represented by the general formula (5) preferably has a structure represented by the following formula (5').
• the thermoplastic resin of one embodiment of the present invention also preferably contains a structural unit derived from at least one monomer selected from the following monomer group.
• R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group
• R 3 and R 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a carbon number 2 ⁇ 5 alkylene glycol
• the polyester carbonate resin of a preferred embodiment of the present invention can be produced by a melt polycondensation method using the dicarboxylic acid or carboxylic diester constituting the structural unit (A), a diol compound, and a carbonic acid diester as raw materials.
• the diol compound include the above-mentioned aliphatic dihydroxy compounds and aromatic dihydroxy compounds, and monomers represented by the above general formula (6) and/or monomers represented by the above general formula (7). are preferred.
• the polycondensation catalyst can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both.
• carbonic acid diesters examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like.
• diphenyl carbonate is particularly preferred from the viewpoint of reactivity and purity.
• the amount of the carbonic acid diester to be added can be determined on the assumption that the diol component and the dicarboxylic acid component react in equimolar amounts, and the remainder reacts with the carbonic acid diester.
• the carbonic acid diester is preferably used in a ratio of 0.60 to 1.50 mol, more preferably 0.80 to 1.40 mol, even more preferably 1 mol, per 1 mol of the difference between the diol component and the dicarboxylic acid component.
• the ratio is from .00 to 1.30 mol, even more preferably from 1.00 to 1.25 mol, particularly preferably from 1.00 to 1.20.
• the molecular weight of the polyester carbonate resin is controlled.
• Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Sodium carbonate and sodium hydrogen carbonate are preferred from the viewpoints of catalytic effect, price, distribution volume, influence on the hue of the resin, and the like.
• Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds.
• Examples of the nitrogen-containing compound include quaternary ammonium hydroxide, salts thereof, and amines.
• salts of zinc, tin, zirconium, and lead are preferably used, and these can be used alone or in combination. It may also be used in combination with the alkali metal compounds and alkaline earth metal compounds mentioned above.
• the transesterification catalyst includes tris(2,4-pentanedionato)aluminum(III), diethyl (4-methylbenzyl)phosphonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, Tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate ( II), lead (IV) acetate, zirconium acetate, titanium tetrabutoxide, etc.
• zinc acetate, zirconium acetate, tris(2,4-pentanedionato)aluminum(III), and diethyl (4-methylbenzyl)phosphonate are preferred; tris(2,4-pentanedionato)aluminum(III) ), and diethyl (4-methylbenzyl)phosphonate are more preferred.
• the metal component in the catalyst is preferably 0.001 ppm to 1000 ppm, more preferably 0.01 ppm to 100 ppm, particularly preferably 0.1 ppm to 100 ppm, relative to the theoretically produced amount of resin. It is used like this.
• the melt polycondensation method is a method in which melt polycondensation is performed using the above-mentioned raw materials and catalysts while removing by-products by transesterification under heating and normal pressure or reduced pressure. Specifically, the reaction is carried out at a temperature of 120 to 260°C, preferably 180 to 260°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the diol compound and carbonic diester are reacted by increasing the reaction temperature while increasing the degree of vacuum in the reaction system, and finally polycondensation is carried out at a temperature of 200 to 350°C for 0.05 to 2 hours under reduced pressure of 1 mmHg or less. Perform a reaction. Such a reaction may be carried out continuously or batchwise.
• the reactor used to carry out the above reaction may be a vertical type equipped with an anchor type stirring blade, a max blend stirring blade, a helical ribbon type stirring blade, etc., or a vertical type equipped with a paddle blade, a lattice blade, a spectacle blade, etc.
• the reactor may be of a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
• the catalyst may be removed or deactivated after the polymerization reaction is completed in order to maintain thermal stability and hydrolytic stability.
• a method of deactivating the catalyst by adding a known acidic substance is preferably carried out.
• these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acids such as butyl p-toluenesulfonate, and hexyl p-toluenesulfonate.
• Esters phosphorous acid, phosphoric acid, phosphoric acids such as phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphite esters such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphoric acid Phosphate esters such as dioctyl and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphospho
• alkyl sulfates such as dimethyl sulfate, organic halides such as dichloride, and the like are preferably used.
• aromatic sulfonate salts such as tetrabutylphosphonium dodecylbenzenesulfonate.
• these deactivators are used in an amount of 0.01 to 50 times the amount of the catalyst, preferably 0.3 to 20 times the amount of the catalyst. If it is less than 0.01 times the amount of the catalyst by mole, the deactivation effect will be insufficient, which is not preferable. Moreover, if the amount is more than 50 times the amount of the catalyst by mole, the heat resistance will decrease and the molded article will be more likely to be colored, which is not preferable.
• a step may be provided to devolatilize and remove low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C.
• a horizontal device equipped with a stirring blade with excellent surface renewal ability, such as a blade, or a thin film evaporator is preferably used.
• the polyester carbonate resin of the present invention has as little foreign matter content as possible, and filtration of the molten raw material and filtration of the catalyst liquid are suitably carried out.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
• the resulting resin is preferably filtered through a polymer filter.
• the mesh of the polymer filter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
• the step of collecting resin pellets must naturally be in a low dust environment, preferably class 1000 or less, more preferably class 100 or less.
• the polyester resin of a preferred embodiment of the present invention can be produced by a conventionally known polyester production method using a dicarboxylic acid or carboxylic acid diester constituting the structural unit (A) and a diol compound.
• Examples include melt polymerization methods such as transesterification and direct esterification, and solution polymerization.
• Examples of the diol compound include the above-mentioned aliphatic dihydroxy compounds and aromatic dihydroxy compounds, and monomers represented by the above general formula (6) and/or monomers represented by the above general formula (7). are preferred.
• transesterification catalysts When producing the polyester resin of the present invention, transesterification catalysts, esterification catalysts, polycondensation catalysts, etc. used in the production of ordinary polyester resins can be used.
• These catalysts are not particularly limited, but include metals such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, germanium, and tin. (eg, fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, alkoxides) and metallic magnesium. These can be used alone or in combination of two or more.
• the amount of these catalysts used is not particularly limited, but the amount as a metal component based on the raw material of the polyester resin is preferably 1 to 1000 ppm, more preferably 3 to 750 ppm, and still more preferably 5 to 500 ppm.
• the reaction temperature in the polymerization reaction depends on the type of catalyst, the amount used, etc., but is usually selected in the range of 150°C to 300°C, and preferably 180°C to 280°C in consideration of the reaction rate and coloring of the resin.
• the pressure within the reaction layer is preferably adjusted to a final value of 1 kPa or less, more preferably 0.5 kPa or less, from atmospheric pressure.
• a phosphorus compound When performing the polymerization reaction, a phosphorus compound may be added if desired.
• the phosphorus compound include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid ester, phosphite ester, and the like.
• Phosphate esters include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, Triethyl phosphate, tributyl phosphate, triphenyl phosphate, etc. can be mentioned.
• Phosphite esters include, but are not limited to, methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, Examples include diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite. These can be used alone or in combination of two or more.
• the concentration of phosphorus atoms in the polyester resin of the present invention is preferably 1 to 500 ppm, more preferably 5 to 400 ppm, even more preferably 10 to 200 ppm.
• various stabilizers such as etherification inhibitors, heat stabilizers, and light stabilizers, polymerization regulators, etc. can be used during the production of the polyester resin in the present invention.
• thermoplastic resin ⁇ Physical properties of thermoplastic resin> (1) Refractive index (nD)
• one of the characteristics of the thermoplastic resin is that it has a high refractive index, and the refractive index is preferably 1.600 to 1.750, and preferably 1.665 to 1.750. More preferably, it is 1.665 to 1.700.
• the refractive index can be measured by the method described in Examples below.
• the Abbe number of the thermoplastic resin is preferably 15.0 to 23.0, more preferably 15.0 to 20.4, and more preferably 16.0 to 20.0. It is particularly preferable that In the present invention, the Abbe number can be measured by the method described in the Examples below.
• one of the characteristics of the thermoplastic resin is that it has high heat resistance
• the glass transition temperature (Tg) is preferably 140 to 180°C, and preferably 147 to 180°C.
• the temperature is more preferably 150 to 175°C, particularly preferably 150 to 175°C.
• the glass transition temperature can be measured by the method described in the Examples below.
• the weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and more preferably 10,000 to 100,000. Particularly preferred is 60,000.
• thermoplastic resin composition containing the above-mentioned thermoplastic resin and an additive.
• the thermoplastic resin composition of the present embodiment may contain resins other than the thermoplastic resin of the present invention containing the above-mentioned structural unit (A), as long as the desired effects of the present embodiment are not impaired.
• resins include, but are not limited to, polycarbonate resins, polyester resins, polyester carbonate resins, (meth)acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, and chlorinated resins.
• Examples include at least one resin selected from the group consisting of vinyl resin, polyphenylene ether resin, polysulfone resin, polyacetal resin, and methyl methacrylate-styrene copolymer resin.
• Various known ones can be used, and one type can be used alone or two or more types can be used in combination to add to the thermoplastic resin composition.
• the thermoplastic resin composition preferably contains an antioxidant as the additive. It is preferable that the antioxidant includes at least one of a phenolic antioxidant and a phosphite antioxidant.
• a phenolic antioxidant 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3 ,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazinee-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1 -methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, ocladecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaeryth, 1,2,4
• phosphite antioxidant 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite, triisodecylphosphite, triphenylphosphite, 3,9-bis(octadecyloxy)-2,4,8,10- Tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenbis(4,6-di-tert-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-tert-butylphenyl) ) phosphite, tris(nonylphenyl)phos
• the antioxidant is preferably contained in an amount of 1 ppm to 3000 ppm by weight based on the total weight of the resin composition.
• the content of the antioxidant in the thermoplastic resin composition is more preferably 50 weight ppm to 2500 weight ppm, still more preferably 100 weight ppm to 2000 weight ppm, particularly preferably 150 weight ppm to 1500 weight ppm. and even more preferably from 200 ppm to 1200 ppm by weight.
• the thermoplastic resin composition preferably contains a mold release agent as the additive.
• a mold release agent ester compounds such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acids, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, aliphatic polyhydric alcohols and aliphatic carboxyls are used. Examples include full esters with acids and monofatty acid esters. When using an ester of an aliphatic polyhydric alcohol and an aliphatic carboxylic acid as a mold release agent, any of monoesters, full esters, etc.
• mold release agents include the following. namely, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan triolate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, sorbitan caprylate; Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; Higher alcohol fatty acid esters such as stearyl stearate; Monoglycerides such as glycerin monostearate, glycerin mono-12-hydroxystearate, glycerin monohydroxystearate, glycerin monooleate, glycerin monobehenate, gly
• the mold release agent is preferably contained in an amount of 1 ppm to 5000 ppm by weight based on the total weight of the resin composition.
• the content of the mold release agent in the thermoplastic resin composition is more preferably 50 weight ppm to 4000 weight ppm, still more preferably 100 weight ppm to 3500 weight ppm, particularly preferably 500 weight ppm to 13000 weight ppm. and even more preferably from 1000 ppm to 2500 ppm by weight.
• additives may be added to the thermoplastic resin composition.
• additives that the thermoplastic resin composition may contain include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust preventives, dispersants, antifoaming agents, leveling agents, Examples include flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents.
• the content of other additives other than the antioxidant and the mold release agent in the thermoplastic resin composition is preferably 10 weight ppm to 5.0 weight %, more preferably 100 weight ppm to 2.0 weight %.
• the content is more preferably 1000 ppm to 1.0% by weight, but is not limited thereto.
• the above-mentioned additives may have an adverse effect on the transmittance, so it is preferable not to add them in excess, for example, the total amount added is within the above-mentioned range.
• thermoplastic resin or thermoplastic resin composition (hereinafter simply referred to as "resin composition") of the present invention can be suitably used for optical members.
• an optical member containing the resin composition of the present invention is provided.
• optical members include optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, etc. Not limited to these.
• the resin composition of the present invention has high fluidity and can be molded by a casting method, so it is particularly suitable for manufacturing thin optical members.
• the optical member manufactured using the resin composition of the present invention may be an optical lens.
• the optical member manufactured using the resin composition of the present invention may be an optical film.
• the molding When producing an optical member containing the resin composition of the present invention by injection molding, it is preferable to perform the molding under conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, the 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 resin composition will decompose and become colored, and if it is lower than 260°C, the melt viscosity will be high and molding will likely become difficult. Further, if the mold temperature is higher than 170° C., it is likely to be difficult to take out the molded piece made of the resin composition from the mold.
• the resin will solidify too quickly in the mold during molding, making it difficult to control the shape of the molded piece, or making it difficult to sufficiently transfer the imprinting pattern on the mold. can easily become difficult.
• the resin composition can be suitably used for optical lenses.
• the optical lens manufactured using the resin composition of the present invention has a high refractive index and is excellent in heat resistance, so expensive high refractive index glass lenses were conventionally used in telescopes, binoculars, television projectors, etc. It can be used in various fields and is extremely useful.
• a lens molded from a resin containing a structural unit derived from any of the monomers of the above formulas can be stacked and used as a lens unit.
• the optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary.
• Aspherical lenses can reduce spherical aberration to virtually zero with a single lens, so there is no need to remove spherical aberration by combining multiple spherical lenses, which reduces weight and molding costs. It becomes possible. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.
• the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for optical lenses that are thin, small, and have complex shapes.
• the thickness at the center is preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and even more 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, and still more preferably 3.0 to 10.0 mm.
• the lens is a meniscus lens in which one side is convex and the other side is concave.
• the optical lens of the present invention can be formed by any method such as molding, cutting, polishing, laser machining, electrical discharge machining, and etching. Among these, molding is more preferable from the viewpoint of manufacturing cost.
• the resin composition can be suitably used for an optical film.
• the optical film produced using the polycarbonate resin of the present invention has excellent transparency and heat resistance, and is therefore suitably used for films for liquid crystal substrates, optical memory cards, and the like.
• the molding environment In order to avoid contamination of foreign matter into the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or lower, more preferably class 5 or lower.
• NMR analysis Measuring device Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) The measurement sample was dissolved in deuterated dimethyl sulfoxide, and the 1 H-NMR spectrum was measured.
• Refractive index Measuring device Refractometer (manufactured by Kyoto Electronics Industry Co., Ltd.: RA-500) Tetrahydrofuran solutions (concentrations of 20%, 15%, and 10% solutions) of measurement samples were prepared, and the refractive index was measured using a refractometer. From the obtained results, the relationship between concentration and refractive index was derived, and the value at 100% concentration was calculated by extrapolation, and this value was taken as the refractive index of the measurement sample.
• Refractometer manufactured by Kyoto Electronics Industry Co., Ltd.: RA-500
• Tetrahydrofuran solutions concentration of 20%, 15%, and 10% solutions
• Powder X-ray diffraction method (PXRD) 0.1 g of the compound obtained in the synthesis example was filled into the sample filling part of a glass test plate, and the measurement was performed using the following apparatus and the following conditions.
• Refractive index (nD) Based on JIS B 7071-2:2018, polycarbonate resin was molded to obtain a V block and used as a test piece. The refractive index was measured at 23° C. using a refractometer (KPR-3000 manufactured by Shimadzu Corporation).
• Low molecular weight compound content The content of low molecular weight compounds represents the area ratio of compounds having an Mw value of less than 1,000 in GPC analysis. Therefore, the content of low molecular weight compounds was determined according to the following formula. GPC analysis is performed as described above to determine the molecular weight of compounds with Mw values less than 1,000.
• the filtered solid was dried at 80° C. under reduced pressure to obtain 33.8 g of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (reaction yield 77.7%)).
• the purity of the obtained target product measured by high performance liquid chromatography was 99.0%.
• the obtained compound was determined to be 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (formula (1a-1-2)) by the following liquid chromatography mass spectrometry and the above 1 H-NMR analysis.
• DSC Differential scanning calorimetry
• Example 1 As raw materials, 3.743 g (0.0085 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the following structural formula, diethyl obtained in Synthesis Example 1, 2'-([9,9'-biphenanthrene]-10,10'-diylbis(oxy)) diacetate (also known as: 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl, abbreviation: BIPOL-DEC) 6.811 g (0.0122 mol), ethylene glycol (EG) 1.135 g (0.0183 mol), manganese (II) acetate tetrahydrate 0.7441 x 10 -3 g (0.3036 x 10 -5 mol) and 0.1244 x 10 -2 g (0.6950 x 10 -5 mol) of calcium acetate monohydrate were placed in a 50 mL reactor equipped with a stirrer
• This reactor was immersed in an oil bath heated to 100°C to start the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and the temperature was raised to 230° C. 120 minutes after the start of the reaction, and maintained for an additional 290 minutes. Thereafter, 0.8794 ⁇ 10 ⁇ 3 g (0.8794 ⁇ 10 ⁇ 5 mol) of phosphoric acid and 0.2398 ⁇ 10 ⁇ 2 g (0.2292 ⁇ 10 ⁇ 4 mol) of germanium dioxide were added to initiate a polycondensation reaction. started. The temperature was raised to 270° C.
• the obtained polyester resin had a refractive index of 1.6910, an Abbe number of 17.5, a Tg of 168.7°C, and a weight average molecular weight (Mw) in terms of polystyrene of 15165.
• Mw weight average molecular weight
• Example 2 A polyester resin was obtained in the same manner as in Example 1, except that the materials shown in Table 2 were used as raw materials. Table 2 shows the composition of the obtained resin and its physical properties.

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