WO2023195504A1 - 熱可塑性樹脂及びそれを含む光学レンズ - Google Patents

熱可塑性樹脂及びそれを含む光学レンズ Download PDF

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WO2023195504A1
WO2023195504A1 PCT/JP2023/014161 JP2023014161W WO2023195504A1 WO 2023195504 A1 WO2023195504 A1 WO 2023195504A1 JP 2023014161 W JP2023014161 W JP 2023014161W WO 2023195504 A1 WO2023195504 A1 WO 2023195504A1
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group
thermoplastic resin
carbon atoms
substituent
general formula
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PCT/JP2023/014161
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English (en)
French (fr)
Japanese (ja)
Inventor
宣之 加藤
克吏 西森
篤志 茂木
健太朗 石原
鈴木 章子 村田
淳広 佐藤
駿 石川
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to EP25193368.5A priority Critical patent/EP4617737A3/en
Priority to JP2024514305A priority patent/JPWO2023195504A1/ja
Priority to US18/852,615 priority patent/US20250223400A1/en
Priority to KR1020247025943A priority patent/KR20240168925A/ko
Priority to CN202380031795.XA priority patent/CN118974141A/zh
Priority to EP23784788.4A priority patent/EP4506392A4/en
Publication of WO2023195504A1 publication Critical patent/WO2023195504A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • 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
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
    • C08G64/1625—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/1666—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing silicon

Definitions

  • the present invention relates to a thermoplastic resin and an optical lens containing the same. More specifically, the present invention relates to a polycarbonate resin, a polyester carbonate resin, or a polyester resin, and an optical lens 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, Abbe's number, and photoelastic coefficient while maintaining heat resistance suitable for use, and an optical lens using the same.
  • thermoplastic resin with excellent optical properties such as refractive index, Abbe number, and photoelastic coefficient, as well as excellent heat resistance, could be obtained by using a monomer having the structure as a raw material, and completed the present invention. I ended up doing it.
  • 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 aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms, each a independently represents 0 or an integer from 1 to 3, and R 3 each independently represents -OH or -O-( CH 2 ) n -OH, where n represents an integer from 1 to 4.) ⁇ 2>
  • n independently represents an integer from 1 to 4. ⁇ 5> The thermoplastic resin according to ⁇ 1> above, wherein the monomer represented by the general formula (1) is a monomer represented by the following formula (15).
  • thermoplastic resin according to any one of ⁇ 1> to ⁇ 5> above, wherein the thermoplastic resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin.
  • 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). , the thermoplastic resin according to any one of ⁇ 1> to ⁇ 6> 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.
  • ⁇ 8> The thermoplastic resin according to ⁇ 7> 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 ⁇ 7> or ⁇ 8> 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 ⁇ 9> above further including 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
  • Mw polystyrene equivalent weight average molecular weight
  • nD refractive index
  • An optical lens comprising the thermoplastic resin according to any one of ⁇ 1> to ⁇ 15> above.
  • thermoplastic resin that has excellent optical properties such as refractive index, Abbe's number, and photoelastic coefficient while maintaining heat resistance suitable for use, and an optical lens containing the thermoplastic resin.
  • FIG. 2 is a diagram showing a chart of differential scanning calorimetry (DSC) data of crystals of the compound obtained in Synthesis Example 2.
  • FIG. 2 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of crystals of the compound obtained in Synthesis Example 2.
  • DSC differential scanning calorimetry
  • PXRD powder X-ray diffraction
  • thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1).
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a hydrogen atom or a carbon number 6 to 14 represents an aryl group or an aralkyl group having 7 to 17 carbon atoms
  • R 3 each independently represents -OH or -O-(CH 2 ) n -OH, where n represents an integer of 1 to 4.
  • R 1 in the general formula (1) each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms;
  • An aryl group or an aralkyl group having 7 to 13 carbon atoms is preferable, each independently an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 11 carbon atoms is more preferable, each independently having 7 to 13 carbon atoms.
  • Aryl groups having 6 to 14 carbon atoms are more preferred, and aryl groups each independently having 6 to 10 carbon atoms are particularly preferred.
  • aryl group having 6 to 14 carbon atoms examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, etc. Among them, phenyl group and naphthyl group are preferable, and phenyl group is more preferable.
  • Examples of aralkyl groups having 7 to 17 carbon atoms include benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group, 1-methyl- Examples include 1-(1-naphthyl)ethyl group, 1-methyl-1-(2-naphthyl)ethyl group, anthracen-9-yl-methyl group, phenanthren-9-yl-methyl group, among others, benzyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group are preferable, benzyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl- A methyl group is more preferred, and a benzyl group is even more preferred.
  • R 1 in general formula (1) it is particularly preferable that both R 1 are
  • R 2 in the general formula (1) each independently represents a hydrogen atom, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and among them, each independently represents a hydrogen atom, An aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 13 carbon atoms is preferable, and each independently a hydrogen atom, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms is more preferable. preferable.
  • the aryl group having 6 to 14 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, etc.
  • phenyl group and naphthyl group are preferable, and phenyl group is more preferable.
  • aralkyl groups having 7 to 17 carbon atoms include benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group, 1-methyl- Examples include 1-(1-naphthyl)ethyl group, 1-methyl-1-(2-naphthyl)ethyl group, anthracen-9-yl-methyl group, phenanthren-9-yl-methyl group, among others, benzyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group are preferred, benzyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl- A methyl group is more preferred, and
  • a in general formula (1) each independently represents 0 or an integer of 1 to 3, each independently preferably 0, 1 or 2, each independently more preferably 0 or 1, and 0 is More preferred.
  • a in the general formula (1) represents an integer of 1 to 3, it is preferable that at least one R 2 is bonded to the ortho position of R 3 .
  • R 3 in general formula (1) each independently represents -OH or -O-(CH 2 ) n -OH.
  • a compound in which R 3 in general formula (1) is -OH is a compound represented by general formula (1A) (compound 1A).
  • R 1 , R 2 and a have the same definitions as in general formula (1).
  • a compound in which R 3 in general formula (1) is -O-(CH 2 ) n -OH is a compound represented by general formula (1B) (compound 1B).
  • R 1 , R 2 , a and n have the same definitions as in general formula (1).
  • Each n in the general formula (1B) independently represents an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 2.
  • ⁇ Monomer manufacturing method-1> Regarding the 1,3-bis(1-methyl-1-phenylethyl)benzene compound represented by the general formula (1) in the present invention, there are no particular limitations on the starting materials and production method.
  • the method for producing compound 1A involves reacting a phenol compound represented by general formula (2) with ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol, as exemplified by the reaction formula below. Examples include manufacturing methods.
  • R 1 , R 2 and a are the same as defined in general formula (1).
  • the phenol compound represented by the general formula (2) includes, for example, 2-phenylphenol, 2-(1-naphthyl)phenol, 2-(2-naphthyl)phenol, 2-(9-anthracenyl) Phenol, 2-(9-phenanthryl)phenol, 2,6-diphenylphenol, 2-benzylphenol, 2-(1-methyl-1-phenylethyl)phenol, 2-(1-naphthylmethyl)phenol, 2-( 2-naphthylmethyl)phenol, 2-(9-anthracenylmethyl)phenol, 2-(9-phenanthrylmethyl)phenol, 2-phenyl-6-benzylphenol, 2-phenyl-6-(1-methoxyphenol) thyl-1-phenylethyl)phenol, 2-phenyl-6-(1-naphthylmethyl)phenol, 2-phenyl-6-(2-naphthylmethyl)phenol, 2-(1-naphthyl)phenol,
  • the amount of the phenol compound represented by general formula (2) is 5 to 5 to 1 mole of ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol.
  • the amount is preferably in the range of 12 mols, more preferably 7 to 10 mols, and even more preferably 8 mols.
  • the above manufacturing method is preferably carried out in the presence of an acid catalyst.
  • Preferred acid catalysts include concentrated hydrochloric acid, sulfuric acid, hydrochloric acid gas, etc. Among them, it is more preferable to use hydrochloric acid gas until the reaction solution is saturated.
  • the reaction is usually carried out in the presence of a solvent. There are no particular limitations on the solvent as long as it does not inhibit the reaction. Since Compound 1A is easily soluble in various solvents, various solvents can be used. Among these, alcohols with good solubility in the phenolic compound represented by general formula (2) are preferred, alcohols having 1 to 10 carbon atoms are more preferred, methanol, ethanol, propanol, and isopropanol are even more preferred, and methanol is particularly preferred.
  • solvents can be used alone or in combination.
  • the amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually in the range of 1 to 5 times the weight of ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol. It is preferably used in a range of 1 to 3 times by weight, more preferably in a range of 1 to 2 times by weight.
  • the above manufacturing method may be carried out either in the air or in an inert gas atmosphere, but in order to suppress coloring of the reaction product, an inert gas atmosphere such as nitrogen or argon is preferable.
  • the reaction temperature is usually in the range of 20 to 40°C, preferably in the range of 25 to 30°C.
  • the reaction may be carried out under normal pressure conditions, increased pressure conditions, or reduced pressure conditions, but it is preferable to carry out the reaction under normal pressure conditions.
  • Compound 1A can be obtained from the reaction mixture by separating and purifying the obtained reaction mixture according to a conventional method. For example, in order to neutralize the acid catalyst, an alkaline aqueous solution such as a sodium hydroxide aqueous solution or an ammonia aqueous solution is added to the reaction completed liquid to neutralize the acid catalyst. The neutralized reaction mixture is allowed to stand, and if necessary, a solvent that separates from water is added to separate and remove the aqueous layer.
  • the target compound 1A can be obtained as a residual liquid.
  • Examples of the method for producing compound 1B include a method in which a compound represented by general formula (1A) and an alkylene oxylating agent are reacted.
  • the reaction formula when carbonates represented by general formula (3) are used as the alkylene oxylating agent is illustrated.
  • R 1 , R 2 , a and n are the same as defined in general formula (1).
  • the compound 1A represented by the general formula (1A) can be a compound obtained by the above production method-1.
  • alkylene oxylating agents include carbonates represented by general formula (3) such as ethylene carbonate, and halogenated alcohols such as 2-chloroethanol and 3-chloro-1-propanol, depending on the target compound. Can be used.
  • carbonates represented by the general formula (3) are used as the alkylene oxylating agent will be described below.
  • the raw material molar ratio of compound 1A and carbonates is usually in the range of about 1/2 to 1/5, preferably in the range of about 1/2 to 1/4, and more preferably in the range of about 1/2 to 1/4. is in the range of about 1/2 to 1/3.
  • a basic catalyst during the reaction, and generally known ones can be used as the basic catalyst. Specifically, quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium chloride, alkali metal halides such as potassium hydroxide, potassium iodide, and sodium bromide, and triorganophosphines such as triphenylphosphine and tributylphosphine.
  • quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium chloride
  • alkali metal halides such as potassium hydroxide, potassium iodide, and sodium bromide
  • triorganophosphines such as triphenylphosphine and tributylphosphine.
  • Examples include amine catalysts such as compounds, 1-methylimidazole, and alkali catalysts such as potassium carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide, sodium hydroxide, sodium hydrogen carbonate, sodium methoxy, and sodium phenoxy.
  • alkali catalysts such as potassium carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide, sodium hydroxide, sodium hydrogen carbonate, sodium methoxy, and sodium phenoxy.
  • These basic catalysts may be used alone or in combination of two or more types.
  • the amount of the basic catalyst used is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, based on the compound 1A represented by the general formula (1A).
  • reaction solvent various known reaction-inactive solvents can be used.
  • reaction solvents include aromatic hydrocarbons such as toluene and xylene, ether solvents such as tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, ketone solvents such as acetone and methyl isobutyl ketone, chloroform, and 1,2-dimethoxyethane.
  • Halogenated hydrocarbons such as dichloroethane, aliphatic alcohols such as butanol and ethylene glycol, and polar solvents such as dimethylformamide and dimethyl sulfoxide.
  • amount of the reaction solvent used is preferably in the range of 0.5 to 10 times, more preferably 0.5 to 5 times by weight, relative to Compound 1A.
  • the above manufacturing method may be carried out either in the air or in an inert gas atmosphere, but in order to suppress coloring of the reaction product, an inert gas atmosphere such as nitrogen or argon is preferable.
  • the reaction temperature is not particularly limited as long as the reaction proceeds, but the reaction is usually carried out under heating.
  • reaction time depends on the reaction temperature, the carbonates used, the amount and type of basic catalyst, etc., but is usually carried out for about 3 to 24 hours. In this reaction, the time when the generation of carbon dioxide gas has stopped can be used as a guideline for the end of the reaction.
  • Compound 1B can be obtained from the reaction mixture by separating and purifying the obtained reaction mixture according to a conventional method.
  • acid-containing water eg, hydrochloric acid, sulfuric acid
  • acetic acid e.g., propionic acid, etc. This neutralization step may be performed after the hydrolysis step described below is performed.
  • the hydrolysis step of carbonates by adding water.
  • the amount of water used is in the range of 1 to 10 times the amount of carbonate used in the above reaction by mole.
  • the temperature may be lower than the boiling point of the reaction liquid, but is usually in the range from room temperature to lower than the boiling point of the reaction liquid. Specifically, the lower limit is 10°C or higher, more preferably 20°C or higher.
  • the upper limit depends on the boiling point of the solvent used, it is preferably 150°C or less.
  • add a solvent that separates from water as needed wash the oil layer multiple times with water, separate and remove the water layer, and remove low-boiling substances such as the solvent by distilling it under reduced pressure from the obtained oil layer.
  • post-treatment operations such as washing with water, crystallization, filtration, distillation, separation by column chromatography, etc., and drying can be performed.
  • further purification by distillation, recrystallization, or column chromatography may be performed according to conventional methods.
  • the crystal of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene represented by the above formula (15) has an endothermic peak determined by differential scanning calorimetry.
  • the peak top temperature of is in the range of 134 to 140°C, more preferably in the range of 135 to 139°C, and particularly preferably in the range of 136 to 139°C. Furthermore, crystals of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene represented by the above formula (15) can be obtained by Cu-K ⁇ radiation. In the powder X-ray diffraction peak pattern, diffraction peaks are found at diffraction angles 2 ⁇ of 7.9 ⁇ 0.2°, 10.8 ⁇ 0.2°, 16.3 ⁇ 0.2° and 18.6 ⁇ 0.2°. There is.
  • the purity of the crystals of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene represented by the above formula (15) is determined by liquid chromatography analysis. In terms of area percentage, it is preferably 90% or more, more preferably 93% or more, even more preferably 95% or more, and particularly preferably 98% or more.
  • Crystals of the compound represented by the above formula (15) can be obtained by precipitating the compound from a solution dissolved in a chain aliphatic ketone solvent having 5 to 8 carbon atoms.
  • the compound used here can be one obtained by the method described above.
  • the compound When precipitating the compound represented by the above formula (15) from a solution dissolved in a chain aliphatic ketone solvent having 5 to 8 carbon atoms, the compound may be precipitated by cooling the solution or distilling off the solvent of the solution.
  • a chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms may be mixed with a solution of the compound in a chain aliphatic ketone solvent having 5 to 8 carbon atoms.
  • chain aliphatic ketone solvents having 5 to 8 carbon atoms include diethyl ketone (5 carbon atoms), methyl isobutyl ketone (6 carbon atoms), methyl amyl ketone (7 carbon atoms), and methylhexyl ketone (7 carbon atoms). 8), among which methyl isobutyl ketone and methyl amyl ketone are preferred.
  • the solution can be washed with water to remove water-soluble impurities such as salts before crystallization.
  • the amount of the chain aliphatic ketone solvent to be used is preferably in the range of 1 to 7 times the weight of the compound represented by the above formula (15), and 1.5 to 6 times the weight of the compound represented by formula (15). It is more preferable that the amount is in the range of 2 to 5 times the weight.
  • the chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, etc. can be used. Cyclic aliphatic hydrocarbon solvents are preferred, and cyclopentane or cyclohexane are more preferred.
  • the amount of the aliphatic hydrocarbon solvent to be used is preferably in the range of 1 to 10 times by weight, and in the range of 1 to 7 times by weight, relative to the amount of the compound represented by formula (15) above. More preferably, the amount is in the range of 1 to 5 times by weight.
  • the temperature at which the chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms is mixed with the chain aliphatic ketone solution having 5 to 8 carbon atoms of the compound represented by the above formula (15) is determined by the temperature used.
  • the temperature is preferably in the range of 60 to 120°C, more preferably in the range of 60 to 100°C, and even more preferably in the range of 60 to 90°C.
  • the temperature at which crystals of the compound represented by formula (15) begin to precipitate is preferably in the range of 10 to 50°C, more preferably in the range of 15 to 40°C.
  • the crystals obtained by the above method may be isolated by a conventional method, for example, the crystals can be isolated by centrifugal filtration. Moreover, it is preferable to further wash the crystals with a solvent. The used solvent can be removed by drying the obtained crystals.
  • thermoplastic resin in one embodiment of the present invention includes, but is not particularly limited to, polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethacrylate resin, etc., but polycarbonate resin, It is preferably a polyester carbonate resin or a polyester resin, and more preferably contains a structural unit (A) represented by the following formula.
  • R 1 , R 2 , and a are the same as defined in general formula (1).
  • 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, 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-hexanediol, etc.
  • 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.
  • 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 contains one or more heterocyclic atoms selected from O, N and S.
  • R a and R b 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.
  • X represents a single bond or a fluorene group which may have a substituent.
  • X is preferably a single bond or a fluorene group which may have a substituent having 12 to 20 carbon atoms in total.
  • 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 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 thermoplastic resin of one embodiment of the present invention has a structural unit (D) derived from a monomer represented by the following general formula (16).
  • the content of the structural unit (D) derived from the monomer represented by general formula (16) is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, of all the structural units. More preferred.
  • 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.
  • L 1 each independently represents a divalent linking group.
  • L 1 is preferably an alkylene group having 1 to 12 carbon atoms which may have a substituent, more preferably an alkylene group having 1 to 5 carbon atoms, and an alkylene group having 2 or 3 carbon atoms. It is more preferable that it is, and it is especially preferable that it is an ethylene group.
  • substituents for the alkylene group of L 1 include alkyl groups, cycloalkyl groups, aryl groups, alkoxyl groups, and combinations thereof. Specific examples of these groups include methyl groups, ethyl groups, n-propyl groups. , isopropyl group, phenyl group, methoxy group, ethoxy group, etc.
  • 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.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom
  • examples of a substituent having 1 to 20 carbon atoms that may contain an aromatic group include a methyl group, a phenyl group, a naphthyl group, a thienyl group
  • Examples of the naphthyl group include 1-naphthyl group and 2-naphthyl group
  • examples of the thienyl group include 2-thienyl group and 3-thienyl group.
  • examples of the benzothienyl group include a 2-benzo[b]thienyl group and a 3-benzo[b]thienyl group. These groups may further have a substituent, and such substituents include, for example, those described above as substituents for the alkylene group of L1 , but are not limited thereto. do not have.
  • j3 and j4 each independently represent an integer from 0 to 4.
  • j3 and j4 are preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • t represents an integer of 0 or 1, and is preferably 1.
  • the monomer represented by the general formula (16) preferably has a structure represented by the following formula (16').
  • alcoholic compounds such as phenolic compounds that may be produced as by-products during production, diol components or carbonic acid diesters that remain unreacted are present as impurities.
  • Impurities such as alcoholic compounds such as phenolic compounds and diester carbonate may cause a decrease in strength or the generation of odor when formed into a molded product, so it is preferable that their content is as small as possible.
  • the content of the remaining phenolic compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, particularly preferably 300 mass ppm or less, based on 100 mass % of the polycarbonate resin.
  • the content of the remaining diol component is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, particularly preferably 10 mass ppm or less, based on 100 mass % of the polycarbonate resin.
  • the content of the remaining diester carbonate is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, particularly preferably 10 mass ppm or less, based on 100 mass % of the polycarbonate resin.
  • the content of compounds such as phenol and t-butylphenol is small, and it is preferable that the content of these compounds is within the above range.
  • the content of the phenolic compound remaining in the polycarbonate resin can be measured by a method of analyzing the phenolic compound extracted from the polycarbonate resin using gas chromatography.
  • the content of alcohol compounds remaining in the polycarbonate resin can also be measured by a method of analyzing alcohol compounds extracted from the polycarbonate resin using gas chromatography.
  • the content of diol components and diester carbonate remaining in the polycarbonate resin can also be measured by extracting these compounds from the polycarbonate resin and analyzing them using gas chromatography.
  • the content of by-product alcoholic compounds such as phenolic compounds, diol components, and carbonic acid diesters may be reduced to such an extent that they are not detected, but from the viewpoint of productivity, they may be contained in small amounts as long as they do not impair the effectiveness. Good too. In addition, if the amount is small, plasticity can be improved when the resin is melted.
  • each of the remaining phenolic compound, diol component, or carbonic acid diester is, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more based on 100 mass % of the polycarbonate resin. You can.
  • the content of the remaining alcoholic compound may be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more based on 100 mass % of the polycarbonate resin.
  • the content of by-product alcohol compounds such as phenolic compounds, diol components, and carbonic acid diesters in the polycarbonate resin is adjusted to be within the above range by appropriately adjusting the polycondensation conditions and equipment settings. It is possible. Moreover, it can also be adjusted by the conditions of the extrusion step after polycondensation.
  • the remaining amount of by-product alcoholic compounds such as phenolic compounds is related to the type of carbonic acid diester used in the polymerization of the polycarbonate resin, the polymerization reaction temperature, the polymerization pressure, and the like. By adjusting these, the residual amount of by-product alcohol compounds such as phenol compounds can be reduced.
  • the content of the remaining by-product alcoholic compound in the obtained polycarbonate resin is 3000 mass ppm or less based on the polycarbonate resin (100 mass %).
  • the content of the remaining alcoholic compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, particularly preferably 300 mass ppm or less, based on 100 mass % of the polycarbonate resin.
  • 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 1.700, and preferably 1.626 to 1.700. It is more preferable that it is, and it is especially preferable that it is 1.630 to 1.650.
  • the refractive index can be measured by the method described in Examples below.
  • the Abbe number of the thermoplastic resin is preferably 22.0 to 26.0, more preferably 23.0 to 26.0, and more preferably 23.0 to 24.7. 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 70 to 200°C, and preferably 100 to 200°C.
  • the temperature is more preferably from 100 to 150°C, even more preferably from 125 to 150°C, even more preferably from 125 to 145°C, and especially from 125 to 140°C. preferable.
  • 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.
  • one of the characteristics of the thermoplastic resin is that it has a low photoelastic coefficient, and the photoelastic coefficient is preferably 25 to 45, and preferably 25 to 38. It is more preferable that it is, and it is especially preferable that it is 30-38.
  • the photoelastic coefficient can be measured by the method described in Examples below.
  • 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 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, mold molding is more preferable from the viewpoint of manufacturing cost.
  • the resin composition can be suitably used for an optical film.
  • the optical film manufactured 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 chloroform (CDCl 3 ), and 13 C-NMR and 1 H-NMR spectra were measured.
  • Refractive index Measuring device Refractometer (manufactured by Kyoto Electronics Industry Co., Ltd.: RA-500) Tetrahydrofuran solutions (concentrations of 30%, 20%, and 10%) 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 30%, 20%, and 10%
  • 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).
  • reaction solution was neutralized with an aqueous sodium hydroxide solution, and the separated aqueous layer was removed.
  • the reaction solution was neutralized with an aqueous sodium hydroxide solution, and the separated aqueous layer was removed.
  • the mixture was allowed to stand and the separated aqueous layer was removed. Thereafter, the obtained oil layer was washed with water twice at an internal temperature of 75° C. to remove sodium chloride produced by neutralization.
  • toluene and 2-phenylphenol in the flask were distilled off under heating and reduced pressure conditions (final flask internal temperature 270°C, internal pressure 0.6 kPa). Thereafter, the residue in the flask was taken out.
  • the yield of the target product in the obtained solid was 89 mol % based on the raw material ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol.
  • the purity measured by high performance liquid chromatography was 91.9%.
  • compound A 1,3-bis[1-methyl-1-(4-hydroxy-3-phenylphenyl)ethyl]benzene (hereinafter referred to as "compound A”) synthesized in Synthesis Example 1 was contained in 36.9 g of the obtained distillation residue. ) was included. The crude yield of compound A based on ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol was 94 mol%.
  • the obtained crystals were determined to be the target compound 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene (hereinafter referred to as "compound B") by NMR analysis. ).
  • the yield of Compound B based on the amount of Compound A used was 77 mol%.
  • 44.3 g of the obtained crystals of compound B (34.0 g as compound B) and 132.9 g of methyl isobutyl ketone were added to a 500 ml four-necked flask equipped with a reflux device, and the temperature of the liquid in the flask was adjusted. The solids were completely dissolved by heating to 75° C. and stirring.
  • DSC Differential scanning calorimetry
  • Table 1 shows the diffraction angle 2 ⁇ (°) of the diffraction peaks that appeared in the powder X-ray diffraction (PXRD) measurement of the crystals of the obtained compound and the peaks with a relative integrated intensity of 30 or more based on the peak with the largest integrated intensity. Shown below.
  • a PXRD measurement chart is shown in FIG.
  • Example 1 As raw materials, 16.694 g (0.0381 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 4-(1- ⁇ 3-[1 -(4-hydroxy-3-phenylphenyl)-isopropyl]phenyl ⁇ -isopropyl)-2-phenylphenol (also known as 1,3-bis[1-methyl-1-(4-hydroxy-3-phenylphenyl)ethyl) ] 8.1361 g (0.0163 mol) of benzene (abbreviation: BisOPP-M), 12.000 g (0.0560 mol) of diphenyl carbonate (DPC), and 20 ⁇ l of a 2.5 ⁇ 10 -2 mol/liter aqueous solution of sodium hydrogen carbonate.
  • BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
  • Example 2 A polycarbonate resin was obtained in the same manner as in Example 1, except that the amounts of raw materials charged were as shown in Table 2. Table 1 shows the physical properties of the obtained resin.
  • Examples 3-4 Comparative Example 2
  • a polycarbonate resin was obtained in the same manner as in Example 1, except that the amounts of raw materials charged were as shown in Table 4.
  • Table 3 shows the physical properties of the obtained resin.
  • BCFL 9,9-bis(4-hydroxy-3-methylphenyl)fluorene
  • Step 2 After blowing phosgene, 1.45 g of p-tert-butylphenol (PTBP) dissolved in 50 ml of dichloromethane was added, stirred vigorously for 7 minutes to emulsify, and then 0.5 ml of triethylamine was added as a polymerization catalyst and polymerized for 30 minutes. I let it happen.
  • TEBAC triethylbenzylammonium chloride
  • a polycarbonate resin was obtained in the same manner. Table 5 shows the physical properties of the obtained resin.

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PCT/JP2023/014161 2022-04-07 2023-04-06 熱可塑性樹脂及びそれを含む光学レンズ Ceased WO2023195504A1 (ja)

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EP25193368.5A EP4617737A3 (en) 2022-04-07 2023-04-06 Thermoplastic resin and optical lens including same
JP2024514305A JPWO2023195504A1 (https=) 2022-04-07 2023-04-06
US18/852,615 US20250223400A1 (en) 2022-04-07 2023-04-06 Thermoplastic resin and optical lens including same
KR1020247025943A KR20240168925A (ko) 2022-04-07 2023-04-06 열가소성 수지 및 그것을 포함하는 광학 렌즈
CN202380031795.XA CN118974141A (zh) 2022-04-07 2023-04-06 热塑性树脂以及包含该树脂的光学透镜
EP23784788.4A EP4506392A4 (en) 2022-04-07 2023-04-06 THERMOPLASTIC RESIN AND OPTICAL LENS COMPRISING SAME

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WO2024122376A1 (ja) * 2022-12-06 2024-06-13 日本化薬株式会社 エポキシ樹脂、硬化性樹脂組成物、硬化物、およびフェノール樹脂
WO2024135717A1 (ja) * 2022-12-22 2024-06-27 三菱瓦斯化学株式会社 熱可塑性樹脂及びそれを含む光学レンズ
WO2024237154A1 (ja) * 2023-05-12 2024-11-21 三菱瓦斯化学株式会社 熱可塑性樹脂及びそれを含む光学レンズ

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US20250110258A1 (en) * 2021-11-30 2025-04-03 Mitsubishi Gas Chemical Company, Inc. Optical lens that contains thermoplastic resin

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WO2024237154A1 (ja) * 2023-05-12 2024-11-21 三菱瓦斯化学株式会社 熱可塑性樹脂及びそれを含む光学レンズ

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EP4506392A4 (en) 2025-05-28
EP4617737A2 (en) 2025-09-17
US20250223400A1 (en) 2025-07-10
EP4617737A3 (en) 2026-02-18
JPWO2023195504A1 (https=) 2023-10-12
KR20240168925A (ko) 2024-12-02
EP4506392A1 (en) 2025-02-12
TW202346410A (zh) 2023-12-01

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