WO2021014962A1 - Résine thermoplastique et élément optique la contenant - Google Patents

Résine thermoplastique et élément optique la contenant Download PDF

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WO2021014962A1
WO2021014962A1 PCT/JP2020/026545 JP2020026545W WO2021014962A1 WO 2021014962 A1 WO2021014962 A1 WO 2021014962A1 JP 2020026545 W JP2020026545 W JP 2020026545W WO 2021014962 A1 WO2021014962 A1 WO 2021014962A1
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formula
thermoplastic resin
group
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bis
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PCT/JP2020/026545
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English (en)
Japanese (ja)
Inventor
達也 大山
恭輔 山田
学 松井
柳田　高恒
安彦 友成
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帝人株式会社
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Priority to JP2021533920A priority Critical patent/JPWO2021014962A1/ja
Priority to CN202080052042.3A priority patent/CN114375313A/zh
Publication of WO2021014962A1 publication Critical patent/WO2021014962A1/fr
Priority to JP2023204224A priority patent/JP2024023510A/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
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses

Definitions

  • the present invention relates to a thermoplastic resin and an optical member containing the thermoplastic resin, particularly an imaging lens.
  • plastic imaging lenses are being used rather than glass.
  • the reason for this is that the lens shape can be made thinner, the aspherical surface can be complicated, and the lens can be mass-produced at low cost.
  • Thermoplastic resin materials are used as optical members such as optical lenses and optical sheets because they are excellent in optical properties, heat resistance, moldability, and the like.
  • Patent Document 2 discloses that polycarbonate made of BHEB has a refractive index of 1.668, and it is required to continue to create a material having a higher refractive index with technological innovation. .. These resins have a high refractive index and are useful as optical materials, but as the molecular structure of the monomer has a rigid structure, the fluidity during molding deteriorates, which causes residual strain due to residual stress after molding. Become. Therefore, there is a demand for a thermoplastic resin that is useful as an optical lens material and has high fluidity.
  • Patent Document 3 reports a polycarbonate made of BHEB having an aryl group introduced therein
  • Patent Document 4 reports a thermoplastic resin made of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene having an aryl group introduced therein.
  • An object of the present invention is to provide a thermoplastic resin which is useful as an optical lens material and has excellent fluidity.
  • the present invention has a higher refractive index than the conventional one. It is an object of the present invention to provide a thermoplastic resin made of an alcohol raw material having a binaphthalene skeleton having a refractive index and a hue suitable for use in an optical member, and an optical lens containing the same.
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, and L 1 and L 2 respectively.
  • Independently indicates a divalent linking group j and k independently indicate an integer of 0 or more, m and n independently indicate 0 or 1, respectively, and W is represented by the following formula (2) or (3). At least one selected from the group to be
  • thermoplastic resin according to item 1 above wherein the repeating unit represented by the formula (1) is 10 mL% or more, and the content of the oligomer having a number average molecular weight of less than 1,500 is 1.0% by mass or more. ..
  • R 1 and R 2 of the formula (1) are any of a hydrogen atom, a phenyl group, a naphthyl group, and a thienyl group.
  • the thermoplastic resin according to any one of the preceding items 1 to 4 wherein the formula (1) is represented by the following formula (1-a) or (1-b).
  • R 1 and R 2 , L 1 and L 2 , m and n, and W are the same as the respective formulas in the above formula (1).
  • thermoplastic resin according to any one of items 1 to 5 above, which contains a repeating unit represented by the following formula (4).
  • ring Z represents the same or different aromatic hydrocarbon ring
  • Ar 1 and Ar 2 represent aromatic groups which may contain a hydrogen atom, a halogen atom and a substituent
  • R 1 and R represent an aromatic group.
  • 2 , L 1 and L 2 , j and k, m and n, W are the same as the respective formulas in the above formula (1).
  • thermoplastic resin according to any one of the above items 1 to 8, wherein the viscosity at a shear rate of 61 (1 / s) at 260 ° C. is 100 (Pa ⁇ s) or more and 1,200 (Pa ⁇ s) or less.
  • the b * value of the CIE1976 (L * a * b *) color system of the solution (a solution in which 1.0 g was dissolved in 5 ml of methylene chloride) dissolved in 13% by mass of the thermoplastic resin in methylene chloride was determined.
  • thermoplastic resin according to item 1 above which has a refractive index of 1.670 or more and 1.740 or less at a wavelength of 589 nm and is 30.0 or less.
  • the thermoplastic resin according to item 10 above which contains 20 mL or more of the repeating unit represented by the formula (1).
  • thermoplastic according to the above item 10 or 11, wherein any one of R 1 and R 2 of the formula (1) is a hydrocarbon group having 1 to 14 carbon atoms which may contain a halogen atom and an aromatic group. resin.
  • thermoplastic resin according to any one of items 10 to 12 above, wherein the formula (1) is represented by the following formula (1-a).
  • thermoplastic resin according to any one of items 10 to 12 above, wherein the formula (1) is represented by the following formula (1-c).
  • ring Z represents the same or different aromatic hydrocarbon ring
  • Ar 1 and Ar 2 represent aromatic groups which may contain a hydrogen atom, a halogen atom and a substituent
  • R 1 and R represent an aromatic group.
  • 2 each independently represent a hydrogen atom, a halogen atom, a divalent linking group independently .
  • L 1 and L 2 is a hydrocarbon group of the aromatic group to contain an carbon atoms which may 1 to 14 Shown, j and k each independently represent an integer of 1 or more, m and n independently represent 0 or 1, respectively, and W is the same as the early equation (1).
  • the thermoplastic resin according to any one of the above items 1 to 17, wherein the specific viscosity of the thermoplastic resin is 0.12 to 0.40.
  • thermoplastic resin according to any one of items 1 to 19 above, wherein the thermoplastic resin is polyester, polyester carbonate, or polycarbonate.
  • thermoplastic resin according to any one of items 1 to 19 above, wherein the thermoplastic resin is polyester or polyester carbonate.
  • optical member according to item 23 which is an optical film.
  • optical member according to item 24 above which is an imaging lens for use in any of mobile phones, smartphones, tablet terminals, personal computers, digital cameras, video cameras, in-vehicle cameras, and surveillance cameras.
  • Example 1 The melt viscosities of Example 1 and Comparative Example 1 at 260 ° C. measured using a Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • thermoplastic resin of the aspect I of the present invention contains 10 mL% or more of the repeating unit represented by the above formula (1), and the content of the oligomer having a number average molecular weight of less than 1,500 is 1.0% by mass or more. Moreover, the refractive index at a wavelength of 589 nm is 1.640 or more and 1.740 or less.
  • the present inventors have 1.0% by mass or more of oligomers having a number average molecular weight of less than 1,500 produced when the above formula (1) is polymerized.
  • the resin has a very high fluidity as compared with the case where there is no oligomer having a number average molecular weight of less than 1,500.
  • an optical lens is molded using such a resin, it has high fluidity and is useful because distortion due to residual stress can be reduced.
  • thermoplastic resins for optical applications it is very difficult to improve the fluidity without changing the composition of the monomer, that is, without changing the optical characteristics, or to increase the fluidity without impairing the mechanical properties.
  • thermoplastic resin The refractive index (nD) of the thermoplastic resin of the present invention at a wavelength of 589 nm measured at 25 ° C. is 1.640 or more and 1.740 or less.
  • the refractive index (nD) may be 1.650 or more, 1.660 or more, 1.670 or more, 1.680 or more or 1.690 or more, and may be 1.740 or less, 1.730 or less, 1.710 or less. Hereinafter, it may be 1.700 or less, 1.695 or less, or 1.690 or less.
  • the refractive index (nD) may be 1.640 or more and 1.740 or less, 1.660 or more and 1.730 or less, or 1.680 or more and 1.720 or less.
  • the Abbe number ( ⁇ ) of the thermoplastic resin of the present invention is, for example, 25.0 or less.
  • ⁇ may be 24.0 or less, 22.0 or less, 20.0 or less, 18.0 or less, 17.0 or less, 16.0 or less, or 15.0 or less, 10.0 or more, 11. It may be 0 or more, 12.0 or more, 13.0 or more, 14.0 or more, 15.0 or more, or 16.0 or more.
  • ⁇ may be 10.0 or more and 25.0 or less, 11.0 or more and 22.0 or less, or 14.0 or more and 18.0 or less.
  • the thermoplastic resin of the present invention has a small degree of coloring and is particularly light in yellow.
  • the b * value of the CIE1976 (L * a * b * ) color system is 10.0 or less, and 8.0 or less, 6.0 or less, 5.0 or less, or 3.0 or less. Preferably, it may be 0.01 or more, 0.1 or more, 1.0 or more, or 3.0 or more.
  • this b * value may be 0.01 or more and 10.0 or less, or 0.1 or more and 5.0 or less.
  • This b * value is a CIE1976 (L * a * b * ) color system value measured with a spectrophotometer for a solution in which 1.0 g is dissolved in 5 ml of dichloromethane (a solution dissolved in dichloromethane at 13% by mass). is there.
  • a palladium catalyst may be used when synthesizing a raw material for a thermoplastic resin for an optical lens.
  • the present inventors consider that the residual amount of the palladium catalyst in the raw material is related to the coloring of the thermoplastic resin. I found that. Then, the present inventors have found that a useful optical lens can be provided by using the above-mentioned thermoplastic resin in which the residual amount of the palladium catalyst is adjusted.
  • the glass transition temperature of the thermoplastic resin of the present invention may be 120 ° C. or higher, 130 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, or 160 ° C. or higher, 190 ° C. or lower, 180 ° C. or lower, 170 ° C. or lower, Alternatively, the temperature may be 160 ° C. or lower.
  • the glass transition temperature is 120 ° C. or higher and 190 ° C. or lower, or 130 ° C. or higher and 170 ° C. or lower. When the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.
  • the specific viscosity of the thermoplastic resin may be 0.10 or more, 0.12 or more, 0.15 or more, 0.18 or more, 0.20 or more, or 0.25 or more, and 0.5 or less. It may be 0.45 or less, 0.4 or less, 0.35 or less, or 0.3 or less.
  • the specific viscosity may be 0.12 or more and 0.40 or less, 0.15 or more and 0.35 or less, or 0.18 or more and 0.30 or less.
  • the specific viscosity is measured at 20 ° C. using a solution of 0.7 g of resin in 100 ml of dichloromethane (a solution of 0.5 mass% in dichloromethane).
  • the melt viscosity of the present invention is such that the viscosity at 9,120 (1 / s) is 20 (Pa ⁇ s) or more and 30 (Pa) when measured at 260 ° C. using Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. ⁇ S) or more, 40 (Pa ⁇ s) or more, 50 (Pa ⁇ s) or more, 60 (Pa ⁇ s) or more, 130 (Pa ⁇ s) or less, 120 (Pa ⁇ s) or less, It may be 100 (Pa ⁇ s) or less, 90 (Pa ⁇ s) or less, and 80 (Pa ⁇ s) or less.
  • the melt viscosity is preferably 20 (Pa ⁇ s) or more and 120 (Pa ⁇ s) or less, more preferably 20 (Pa ⁇ s) or more and 100 (Pa ⁇ s) or less, and 25 (Pa ⁇ s) or more and 80 (Pa ⁇ s) or more. s) or less is more preferable, 30 (Pa ⁇ s) or more and 80 (Pa ⁇ s) or less is particularly preferable, and 30 (Pa ⁇ s) or more and 70 (Pa ⁇ s) or less is most preferable.
  • the melt viscosity is preferably 20 (Pa ⁇ s) or more and 120 (Pa ⁇ s) or less, more preferably 20 (Pa ⁇ s) or more and 100 (Pa ⁇ s) or less, and 25 (Pa ⁇ s) or more and 80 (Pa ⁇ s) or more. s) or less is more preferable, 30 (Pa
  • the viscosity at 61 (1 / s) when measured at 260 ° C. may be 100 (Pa ⁇ s) or more, 130 (Pa ⁇ s) or more, 150 (Pa ⁇ s) or more. , 200 (Pa ⁇ s) or less, 1,000 (Pa ⁇ s) or less, 800 (Pa ⁇ s) or less, 600 (Pa ⁇ s) or less, 400 (Pa ⁇ s) or less.
  • the melt viscosity is preferably 100 (Pa ⁇ s) or more and 1,100 (Pa ⁇ s) or less, more preferably 130 (Pa ⁇ s) or more and 600 (Pa ⁇ s) or less, and 150 (Pa ⁇ s) or more and 500 ( Pa ⁇ s) or less is particularly preferable, and 200 (Pa ⁇ s) or more and 500 (Pa ⁇ s) or less is most preferable.
  • the melt viscosity at 61 (1 / s) at the molding temperature of 260 ° C. is within the above range, the fluidity is good and the moldability is excellent, which is preferable. It is preferable that the range is the same even when measured at 280 ° C.
  • the thermoplastic resin of the present invention include polyester, polyester carbonate, and polycarbonate.
  • thermoplastic resin of the present invention contains a repeating unit of the following formula (1).
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group
  • L 1 and L 2 are respectively.
  • j and k independently indicate an integer of 0 or more
  • m and n independently indicate 0 or 1, respectively
  • W is represented by the following formula (2) or (3). At least one selected from the group to be
  • the repeating unit of the above formula (1) is 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, 40 mol% or more, 45 mol% or more. It may be contained in an amount of 50 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 55 mol% or less, 50 mol% or less. Good.
  • the resin of the present invention can contain the repeating unit of the above formula (A) in an amount of preferably 30 mol% or more and 90 mol% or less, more preferably 40 mol% or more and 80 mol% or less. Within the above range, the amount of oligomers having a number average molecular weight of less than 1500 can be contained in a certain amount or more, and the fluidity is improved.
  • the repeating unit represented by the formula (1) is particularly preferably a unit represented by the following formula (1-a) or (1-b).
  • R 1 and R 2 , L 1 and L 2 , j and k, m and n, W are the same as each formula in the above formula (1), but independently of the above formula (1). You may choose.
  • R 1 and R 2 , L 1 and L 2 , j and k, m and n, and W are the same as those in the formula (1), and R 3 and R 4 are R 1 and R, respectively. Same as 2. However, it may be selected independently of the above equation (1).
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, and are a hydrogen atom and a methyl group. , Or a phenyl group or a naphthyl group is preferable.
  • the "aromatic group” is not limited to an aromatic group formed only of a carbon atom and a hydrogen atom, but also includes a heteroaromatic group containing a hetero atom, unless otherwise specified.
  • the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the "aromatic group” includes a monocyclic aromatic group and a condensed polycyclic aromatic group unless otherwise specified.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.
  • hydrocarbon group examples include an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a naphthyl group, and a thienyl group.
  • alkyl group examples include C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group, C 1-4 alkyl group and C 1-3 alkyl group. Is preferable, C 1-4 alkyl group and C 1-3 alkyl group are more preferable, C 1-3 alkyl group is more preferable, and methyl group or ethyl group is more preferable among them.
  • cycloalkyl group a C 5-8 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a C 5-6 cycloalkyl group and the like are preferable, and a C 5-6 cycloalkyl group is more preferable.
  • a C 6-10 aryl-C 1-4 alkyl group such as a benzyl group and a phenethyl group can be preferably exemplified.
  • a phenyl group an alkylphenyl group (mono or dimethylphenyl group (tolyl group, 2-methylphenyl group, xsilyl group, etc.)) and the like are preferable, and a phenyl group is more preferable.
  • a 1-naphthyl group or a 2-naphthyl group is preferable.
  • thienyl group a 2-thienyl group or a 3-thienyl group is preferable.
  • R 1 and R 2 are preferably a hydrogen atom, a phenyl group, a naphthyl group and a thienyl group, and more preferably a hydrogen atom, a phenyl group and a naphthyl group.
  • L 1 and L 2 each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an ethylene group.
  • the glass transition temperature of the resin can be adjusted by adjusting the lengths of the linking groups of L 1 and L 2 .
  • W is at least one selected from the group represented by the formula (2) or (3).
  • W is the formula (2)
  • the formula (1) is a carbonate unit
  • W is the formula (3)
  • the formula (1) is an ester unit.
  • X represents a divalent linking group, and is preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain an aromatic group.
  • the thermoplastic resin of the present invention may contain the repeating unit of the formula (4) represented by the following in an amount of 10 mol% or more, 20 mol% or more, or 30 mol% or more. Further, the upper limit may be included in 90 mol% or less, 80 mol% or less, and 70 mol% or less.
  • the repeating unit represented by the formula (4) is in the above range, it is easy to obtain a resin having a high refractive index, low birefringence, and a balance between heat resistance and moldability. ..
  • ring Z represents the same or different aromatic hydrocarbon ring
  • Ar 1 and Ar 2 represent aromatic groups which may contain a hydrogen atom, a halogen atom and a substituent
  • R 1 and R represent an aromatic group.
  • 2 , L 1 and L 2 , j and k, m and n, W are the same as the respective formulas in the above formula (1), but may be selected independently of the above formula (1).
  • the repeating unit represented by the above formula (4) is particularly preferably a unit represented by the following formula (4-a) or (4-b):
  • Examples of the aromatic hydrocarbon ring represented by the ring Z in the above formula (4) include a fused polycyclic aromatic hydrocarbon ring having at least a benzene ring skeleton in addition to the benzene ring, and for example, a condensed bicyclic ring. Condensed two- to four-cyclic hydrocarbon rings such as a hydrocarbon ring and a condensed tricyclic hydrocarbon ring are preferable.
  • condensed bicyclic hydrocarbon ring C 8-20 such as an indene ring and a naphthalene ring is preferable, and a C 10-16 condensed bicyclic hydrocarbon ring is more preferable.
  • condensed tricyclic hydrocarbon ring an anthracene ring, phenanthrene ring and the like are preferable.
  • a benzene ring and a naphthalene ring are preferable.
  • a 1,4-phenylene group, a 1,4-naphthalene diyl group or a 2,6-naphthalene diyl group is preferable, and 1, A 4-phenylene group or a 2,6-naphthalenediyl group is more preferable.
  • Ar 1 and Ar 2 are monocyclic aromatic groups or condensed polycyclic groups having 1 to 10 carbon atoms which may independently contain a hydrogen atom, a halogen atom and a substituent.
  • a 5- or 6-membered heteroaromatic group which may contain an aromatic group or a substituent or a condensed heteroaromatic group containing the same may be indicated, and the aromatic group having 1 to 10 carbon atoms thereof may be used.
  • a phenyl group or a naphthyl group which may contain a substituent is preferable.
  • the bond positions of Ar 1 and Ar 2 are preferably the 2nd and 7th positions, or the 3rd and 6th positions of the fluorene skeleton, respectively, at the 2nd and 7th positions. It is even more preferable to have it.
  • the heteroaromatic group is preferably a 5- or 6-membered heteroaromatic group or a condensed heteroaromatic group containing the same, and examples of the heteroatom include an oxygen atom, a sulfur atom and a nitrogen atom.
  • sulfur atoms can be mentioned.
  • Ar 1 and Ar 2 are preferably a hydrogen atom, a phenyl group, a naphthyl group and a thienyl group, and more preferably a hydrogen atom, a phenyl group and a naphthyl group.
  • R 1 and R 2 , L 1 and L 2 , W, m, n, j and k are the same as the respective formulas in the above formula (1). However, it may be selected independently of the equation (1).
  • the thermoplastic resin may have other repeating units to the extent that the properties of the present invention are not impaired.
  • the other repeating unit is preferably less than 30 mol%, 20 mol% or less, 10 mol% or less, or 5 mol% or less in all the repeating units.
  • thermoplastic resin containing the unit represented by the above formula (1) produces oligomers as the following formulas (6) to (8) as by-products.
  • the molecular weight distribution of the polymer is small in the resin after polymerization, but in the present invention, a trace amount of oligomer components having a number average molecular weight of less than 1,500 is used. It was found that a resin having excellent fluidity can be obtained by including it.
  • the "oligomer having a number average molecular weight of less than 1,500” means that the molecular weight distribution is measured by the method described in Examples using gel permeation chromatography (GPC), and the number average molecular weight in the entire distribution is Indicates an area ratio (%) of less than 1,500. Since the molecular structure of the unit constituting the high molecular weight component is the same, it is considered that the oligomer can be detected in the same manner at UV 254 nm. Therefore, this area ratio (%) can be converted into mass%. Therefore, in the present application, the area ratio (%) is expressed as mass%.
  • GPC gel permeation chromatography
  • oligomers having a number average molecular weight of less than 1,500 will be shown, but oligomers having a number average molecular weight of less than 1,500 are not limited thereto.
  • R 1 , R 2 , L 1 , L 2 , m, n, j, and k are the same as the respective formulas in the formula (1).
  • R 1 , R 2 , L 1 , L 2 , m, n, j, and k are the same as those in the formula (1), and R 3 and R 4 are independent of each other. It represents a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, L 3 and L 4 each independently represent a divalent linking group, and p and q are respectively. Independently indicates 0 or 1, and l and h independently indicate integers of 0 or more.
  • thermoplastic resin of the present invention preferably contains an oligomer component having a number average molecular weight of less than 1,500 in a volume of 1.0% by mass or more, more preferably 1.5% by mass or more and 15.0% by mass or less. More preferably, it is contained in a volume of 2.0% by mass or more and 12.0% by mass or less.
  • the amount of oligomers that function as a plasticizer is reduced, resulting in lower fluidity. If it is more than the upper limit, the plasticizer lowers the glass transition temperature, and it is presumed that the heat resistance is lowered.
  • thermoplastic resin of the present invention can achieve both mechanical properties and fluidity by controlling the number of oligomers having a number average molecular weight of less than 1,500 without lowering the molecular weight of the high molecular weight component in the thermoplastic resin. I found it.
  • these oligomers in the present invention have a high molecular weight, they do not sublimate at a molding temperature of 300 ° C. or lower, and the possibility of mold contamination during injection molding is low.
  • An oligomer component having a number average molecular weight of less than 1,500 is more likely to be produced as the amount of the diol component or dicarboxylic acid component used as the raw material of the above formula (1) increases, and either one of them, or a total of 40 mL% or more and 99 mL or less. More preferably, it is 50 mL% or more and 95 mL% or less, and further preferably 60 mL% or more and 90 mL% or less, the oligomer component having a number average molecular weight of less than 1,500 is adjusted in the range of 1.0 mass% or more. Cheap.
  • Examples of the method for adjusting the volume of the oligomer component having a number average molecular weight of less than 1,500 to 1.0% by mass or more include a method of adjusting the molar ratio of the raw materials, a method of adjusting the reaction temperature, and a method of adjusting the melting time.
  • ⁇ Raw material for thermoplastic resin> (Diol component of formula (1))
  • the diol component used as a raw material of the formula (1) is mainly a diol component represented by the formula (a), and may be used alone or in combination of two or more.
  • R 1 , R 2 , L 1 , L 2 , m, n, j, and k are the same as the respective equations in the above equation (1).
  • R 1 and R 2 are hydrogen atoms
  • 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (hereinafter, also referred to as "BHEB”) or the like is used as the diol component of the formula (a). Can be mentioned.
  • the diol component of the formula (a) is 2,2'-bis (2-hydroxyethoxy) -3,3'-diphenyl-1,1'. -Binaphthalene, 2,2'-bis (2-hydroxyethoxy) -4,4'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -5,5'-diphenyl- 1,1'-Binaphthalene, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene (hereinafter, also referred to as "BHEB6”), 2,2'-bis (hereinafter, also referred to as "BHEB6") 2-Hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -8,8'-dipheny
  • the diol component of the formula (a) is 2,2'-bis (2-hydroxyethoxy) -3,3'-di (1-naphthyl).
  • the diol component of the formula (a) is (a-3): 2,2'-bis (2-hydroxyethoxy) -6,6'-.
  • Di (2-thienyl) -1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -6,6'-di (3-thienyl) -1,1'-binaphthalene and the like can be mentioned.
  • the following formula (a-3) : 2,2'-bis (2-hydroxyethoxy) -6,6'-di (2-thienyl) -1,1'-binaphthalene is preferable.
  • R 1 and R 2 are phenyl groups and j and k are 2, as the diol component of the formula (a), (a-4): 2,2'-bis (2-hydroxyethoxy) -4,4', 6,6'-Tetraphenyl-1,1'-Binaphthalene and the like can be mentioned.
  • diol component represented by the formula (a) examples include BHEB, BHEB6, 2,2'-bis (2-hydroxyethoxy) -4,4', 6,6'-tetraphenyl-1,1'-binaphthalene. It is preferable, more preferably BHEB, BHEB6.
  • the diol component used as a raw material of the formula (4) is mainly a diol component represented by the formula (b), and may be used alone or in combination of two or more.
  • the rings Z, R 1 , R 2 , Ar 1 , Ar 2 , L 1 , L 2 , j, k, m and n are the same as the respective formulas in the formula (4).
  • the diol component of the formula (b) is, for example, 9,9-bis (4- (2-hydroxyethoxy) phenyl) of the following formula (b-15). ) -2,7-Di (2-thienyl) fluorene can be mentioned.
  • the following formula (b-16) 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (hereinafter, also referred to as "BNEF”) ,
  • BNEF 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene
  • (b-18) 9,9-bis (6- (2-Hydroxyethoxy) -2-naphthyl) -2,7-di (2-naphthyl) fluorene can be mentioned.
  • Examples of the diol component represented by the formula (b) include BPEF, BOPPEF, BPDP2, BPDN1, BPDN2, and the above formula (b-15): 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2.
  • thermoplastic resin may be copolymerized with other diol components to the extent that the characteristics of the present invention are not impaired.
  • the other diol component is preferably less than 30 mol%, 20 mol% or less, 10 mol% or less, or 5 mol% or less in all repeating units.
  • thermoplastic resin examples include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and tricyclo [5.2.1.0 2,6.
  • the dicarboxylic acid component used in the unit represented by the formula (1) or the formula (4) of the thermoplastic resin is mainly a dicarboxylic acid represented by HOOC-X-COOH or an ester-forming derivative thereof. Be done.
  • X represents a divalent linking group for giving a unit represented by the formula (1) or the formula (4).
  • a typical example of the dicarboxylic acid represented by the formula HOOC-X-COOH or an ester-forming derivative thereof is that the diols of the formulas (a) and (b) of the present invention form a dicarboxylic acid or an ester-forming derivative thereof. You can list what you are doing.
  • the dicarboxylic acid component used in the thermoplastic resin includes an aliphatic dicarboxylic acid component such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, and phthal.
  • an aliphatic dicarboxylic acid component such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, and phthal.
  • Monocyclic aromatic dicarboxylic acid components such as acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracendicarboxylic acid, phenanthrenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthalene (hereinafter, also referred to as "BCMB”), 9,9-bis (carboxy) Methyl) fluorene, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (1-carboxyethyl) fluorene, 9,9-bis (1-carboxypropyl) fluorene, 9,9-bis (2) -Carboxypropyl) fluorene
  • Examples include an acid component, a biphenyldicarboxylic acid component such as 2,2'-biphenyldicarboxylic acid, and an alicyclic dicarboxylic acid component such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalindicarboxylic acid, and isophthalic acid and terephthalic acid.
  • 2,6-naphthalenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthalene are preferable. These may be used alone or in combination of two or more types.
  • thermoplastic resin of the present invention is produced by a polyester carbonate resin, and the polyester resin is produced by a reaction means known per se for producing an ordinary resin, for example, in the case of polycarbonate, a dihydroxy compound is reacted with a carbonate precursor such as a carbonic acid diester. Will be done.
  • Thermoplastic resin-impurities> (Residual phenol)
  • the residual phenol content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 400 ppm, still more preferably 1 to 300 ppm.
  • the phenol content is preferably adjusted by the reaction time at a pressure of 1.3 kPa or less. If the reaction is not carried out at a degree of vacuum of 1.3 kPa or less, the phenol content is high. Further, if the reaction time is too long, it will be distilled off too much from the resin.
  • the phenol content may be adjusted after obtaining the thermoplastic resin.
  • a method of dissolving a thermoplastic resin in an organic solvent and washing the organic solvent layer with water a commonly used single-screw or twin-screw extruder, and a kneading device such as various kneaders, 133 to 13.3 Pa.
  • a method of volatilizing and removing at a pressure of 200 to 320 ° C. may be used.
  • the content of residual phenol is appropriate, the molding fluidity can be improved without impairing the heat resistance.
  • the thermal stability when the resin is heated and melted is improved, and mold contamination during resin injection molding can be prevented.
  • thermoplastic resin does not contain a palladium catalyst.
  • the amount of residual palladium catalyst in the thermoplastic resin is preferably 10 ppm or less, more preferably 5.0 ppm or less, 3.0 ppm or less, 1.0 ppm or less, or 0.5 ppm, and more preferably 0.0 ppm or more. It may be 0.1 ppm or more, 0.2 ppm or more, or 0.5 ppm or more. If the amount of residual palladium catalyst in the thermoplastic resin is appropriate, coloring of the resin can be prevented.
  • the palladium catalyst is used as a catalyst for binding an aromatic substituent to a binaphthalene-based component unit or a fluorene-based component unit, and a side chain of a binaphthalene-based component unit or an aromatic substituent containing an aromatic substituent is used.
  • a thermoplastic resin containing a fluorene-based component unit contained in it usually remains.
  • the present inventors have found that the residual amount of the palladium catalyst is related to the coloring of the thermoplastic resin.
  • the monomer containing the palladium catalyst residue and / or the resin thereof can be subjected to a depalladium treatment.
  • the residual binaphthol content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 300 ppm, still more preferably 1 to 100 ppm, and particularly preferably 1 to 50 ppm. If the content of residual binaphthol in the thermoplastic resin is appropriate, coloring of the resin can be prevented.
  • the residual fluorenone content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 300 ppm, still more preferably 1 to 100 ppm, and particularly preferably 1 to 50 ppm. If the content of residual fluorenone in the thermoplastic resin is appropriate, coloring of the resin can be prevented.
  • the optical member of the present invention contains the above-mentioned thermoplastic resin.
  • Such an optical member is not particularly limited as long as it is an optical application in which the above-mentioned thermoplastic resin is useful, but is not limited to an optical fiber, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, and an optical film. , Substrate, optical filter, hard coat film and the like. Examples of the film include an optical film.
  • the optical member of the present invention may be composed of a resin composition containing the above-mentioned thermoplastic resin, and the resin composition may contain, if necessary, a heat stabilizer, a plasticizer, a light stabilizer, and the like. Additives such as polymerized metal inactivating agents, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, and mold release agents can be blended.
  • An image pickup lens can be mentioned as an optical member of the present invention. Examples of such an imaging lens include imaging lenses for mobile phones, smartphones, tablet terminals, personal computers, digital cameras, video cameras, in-vehicle cameras, surveillance cameras, and the like.
  • the imaging lens of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is particularly suitable.
  • the molding conditions for injection molding are not particularly limited, but the cylinder temperature of the molding machine is preferably 180 to 320 ° C, more preferably 220 to 300 ° C, and particularly preferably 240 to 280 ° C.
  • the mold temperature is preferably 70 to 130 ° C, more preferably 80 to 125 ° C, and particularly preferably 90 to 120 ° C.
  • the injection pressure is preferably 5 to 170 MPa, more preferably 50 to 160 MPa, and particularly preferably 100 to 150 MPa.
  • the optical lens of the aspect II of the present invention is an optical lens containing a thermoplastic resin containing a repeating unit represented by the following formula (1), and the thermoplastic resin is dissolved in methylene chloride in an amount of 13% by mass.
  • the CIE1976 (L * a * b * ) color system b * value of the solution (1.0 g dissolved in 5 ml methylene chloride) is 30.0 or less, and the refractive index at a wavelength of 589 nm is 1. It is .670 or more and 1.740 or less.
  • thermoplastic resin used in the optical lens of the present invention is excellent in that it has a high refractive index and a small degree of coloring.
  • refractive index (nD) of the thermoplastic resin of the present invention at a wavelength of 589 nm measured at 25 ° C. is 1.670 or more and 1.740 or less.
  • nD may be 1.670 or more, 1.680 or more or 1.690 or more, 1.740 or less, 1.730 or less, 1.720 or less, 1.710 or less, 1.700 or less, 1. It may be 695 or less, or 1.690 or less.
  • nD is 1.670 or more and 1.740 or less, 1.680 or more and 1.740 or less, 1.690 or more and 1.740 or less, or 1.680 or more and 1.730 or less, 1.680 or more and 1.720 or less. It may be.
  • the thermoplastic resin of the present invention is polyester or polyester carbonate
  • the ratio of carbonate bonds to the binding species constituting the thermoplastic resin is zero or lower than that of polycarbonate. This makes it possible to avoid a decrease in the refractive index for one oxygen atom, resulting in a thermoplastic resin having a higher refractive index.
  • the b * value of the CIE1976 (L * a * b *) color system of the thermoplastic resin of the present invention is 30.0 or less, 20.0 or less, 10.0 or less, 8.0 or less, 6.0 or less, It may be 5.0 or less, 3.0 or less, 0 or more, 0.1 or more, 1.0 or more, or 3.0 or more.
  • the b * value is preferably 0 or more and 30.0 or less, more preferably 0 or more and 20.0 or less, further preferably 0 or more and 10.0 or less, particularly preferably 0 or more and 8.0 or less, and 0 or more and 6.0. The following are the most preferable.
  • This b * value is a value of the CIE1976 (L * a * b * ) color system of a solution in which 1.0 g is dissolved in 5 ml of methylene chloride (a solution dissolved in methylene chloride at 13% by mass).
  • a palladium catalyst may be used when synthesizing a raw material for a thermoplastic resin for an optical lens.
  • the present inventors have found that the residual palladium component derived from the palladium catalyst in the raw material causes coloring of the thermoplastic resin. I found that it was related to. Then, the present inventors have found that a useful optical lens can be provided by using the above-mentioned thermoplastic resin in which the residual amount of the palladium component is adjusted.
  • the glass transition temperature of the thermoplastic resin of the present invention may be 120 ° C. or higher, 130 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, or 160 ° C. or higher, 190 ° C. or lower, 180 ° C. or lower, 170 ° C. or lower, Alternatively, the temperature may be 160 ° C. or lower.
  • the glass transition temperature is 120 ° C. or higher and 190 ° C. or lower, or 130 ° C. or higher and 170 ° C. or lower. When the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.
  • the specific viscosity of the thermoplastic resin of the present invention may be 0.10 or more, 0.12 or more, 0.15 or more, 0.18 or more, 0.20 or more, or 0.25 or more, and may be 0.5. Hereinafter, it may be 0.45 or less, 0.4 or less, 0.35 or less, or 0.3 or less.
  • the specific viscosity may be 0.12 or more and 0.40 or less, 0.15 or more and 0.35 or less, or 0.18 or more and 0.30 or less. When the specific viscosity is in such a range, it is preferable because the balance between moldability and mechanical strength is excellent.
  • the specific viscosity is measured at 20 ° C.
  • thermoplastic resin of the present invention examples include polyester, polyester carbonate, and polycarbonate.
  • thermoplastic resin of the present invention contains a repeating unit of the following formula (1).
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group
  • L 1 and L 2 are respectively.
  • j and k each independently represent an integer of 1 or more
  • m and n independently represent 0 or 1, respectively
  • W is represented by the following formula (2) or (3). At least one selected from the group to be
  • thermoplastic resin of the present invention may contain the repeating unit of the above formula (1) in an amount of 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, and 100 mol%.
  • it may be contained in an amount of 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less.
  • the thermoplastic resin may contain the repeating unit of the above formula (1) in an amount of 20 mol% or more and 100 mol% or less, or 30 mol% or more and 100 mol% or less.
  • the repeating unit represented by the formula (1) is preferably a unit represented by the following formula (1-a) or (1-c). Further, the unit represented by the following formula (1-c) is preferable because the polarizability per repeating unit is improved and a thermoplastic resin having a higher refractive index can be obtained.
  • R 1 and R 2 , L 1 and L 2 , m and n, and W are the same as the respective formulas in the above formula (1).
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 14 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, and are a hydrogen atom and a methyl group. , Or a phenyl group, a naphthyl group, or a thienyl group is preferable.
  • the "aromatic group” is not limited to an aromatic group formed only of a carbon atom and a hydrogen atom, but also includes a heteroaromatic group containing a hetero atom, unless otherwise specified.
  • the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the "aromatic group” includes a monocyclic aromatic group and a condensed polycyclic aromatic group unless otherwise specified.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.
  • hydrocarbon group examples include an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a naphthyl group, and a thienyl group.
  • alkyl group examples include C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group, more preferably C 1-4 alkyl group, and C 1 -3 Alkyl groups are even more preferred, of which methyl or ethyl groups are even more preferred.
  • cycloalkyl group a C 5-8 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a C 5-6 cycloalkyl group and the like are preferable, and a C 5-6 cycloalkyl group is more preferable.
  • a C 6-10 aryl-C 1-4 alkyl group such as a benzyl group and a phenethyl group can be preferably exemplified.
  • a phenyl group an alkylphenyl group (mono or dimethylphenyl group (tolyl group, 2-methylphenyl group, xsilyl group, etc.)) and the like are preferable, and a phenyl group is more preferable.
  • a 1-naphthyl group or a 2-naphthyl group is preferable.
  • thienyl group a 2-thienyl group or a 3-thienyl group is preferable.
  • R 1 and R 2 is preferably a hydrocarbon group having 1 to 14 carbon atoms which may contain a halogen atom and an aromatic group.
  • R 1 and R 2 are preferably a phenyl group, a naphthyl group and a thienyl group, and more preferably a phenyl group and a naphthyl group.
  • L 1 and L 2 each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an ethylene group.
  • the glass transition temperature of the resin can be adjusted by adjusting the lengths of the linking groups of L 1 and L 2 .
  • W is at least one selected from the group represented by the formula (2) or (3).
  • W is the formula (2)
  • the formula (1) is a carbonate unit
  • W is the formula (3)
  • the formula (1) is an ester unit.
  • X represents a divalent linking group, and is preferably a hydrocarbon group having 1 to 30 carbon atoms which may contain an aromatic group.
  • the thermoplastic resin of the present invention may contain the repeating unit of the formula (5) represented by the following in an amount of 10 mol% or more, 20 mol% or more, or 30 mol% or more. Further, the upper limit may be included in 80 mol% or less and 70 mol% or less. When the repeating unit represented by the following formula (5) is in the above range, it is easy to obtain a resin having a high refractive index, low birefringence, and a balance between heat resistance and moldability. ..
  • ring Z represents the same or different aromatic hydrocarbon ring
  • Ar 1 and Ar 2 represent aromatic groups which may contain a hydrogen atom, a halogen atom and a substituent
  • R 1 and R represent an aromatic group.
  • 2 , L 1 and L 2 , j and k, m and n, W are the same as the respective formulas in the above formula (1), but may be selected independently of the above formula (1).
  • the repeating unit represented by the above formula (5) is particularly preferably a unit represented by the following formula (5-a) or (5-b):
  • Examples of the aromatic hydrocarbon ring represented by the ring Z in the above formula (5) include a fused polycyclic aromatic hydrocarbon ring having at least a benzene ring skeleton in addition to the benzene ring, and for example, a condensed bicyclic ring. Condensed two- to four-cyclic hydrocarbon rings such as a hydrocarbon ring and a condensed tricyclic hydrocarbon ring are preferable.
  • condensed bicyclic hydrocarbon ring C 8-20 such as an indene ring and a naphthalene ring is preferable, and a C 10-16 condensed bicyclic hydrocarbon ring is more preferable.
  • fused tricyclic hydrocarbon ring an anthracene ring, a phenanthrene ring and the like are preferable.
  • a benzene ring and a naphthalene ring are preferable.
  • a 1,4-phenylene group, a 1,4-naphthalene diyl group or a 2,6-naphthalene diyl group is preferable, and 1, A 4-phenylene group or a 2,6-naphthalenediyl group is more preferable.
  • Ar 1 and Ar 2 are monocyclic aromatic groups or condensed polycyclic groups having 1 to 10 carbon atoms which may independently contain a hydrogen atom, a halogen atom and a substituent.
  • a 5- or 6-membered heteroaromatic group which may contain an aromatic group or a substituent or a condensed heteroaromatic group containing the same may be indicated, and the aromatic group having 1 to 10 carbon atoms thereof may be used.
  • a phenyl group or a naphthyl group which may contain a substituent is preferable.
  • the bond positions of Ar 1 and Ar 2 are preferably the 2nd and 7th positions, or the 3rd and 6th positions of the fluorene skeleton, respectively, at the 2nd and 7th positions. It is even more preferable to have it.
  • the heteroaromatic group is preferably a 5- or 6-membered heteroaromatic group or a condensed heteroaromatic group containing the same, and examples of the heteroatom include an oxygen atom, a sulfur atom and a nitrogen atom.
  • sulfur atoms can be mentioned.
  • Ar 1 and Ar 2 are preferably a hydrogen atom, a phenyl group, a naphthyl group and a thienyl group, and more preferably a hydrogen atom, a phenyl group and a naphthyl group.
  • R 1 and R 2 , L 1 and L 2 , W, m, n, j and k are the same as the respective formulas in the above formula (1). However, it may be selected independently of the equation (1).
  • the thermoplastic resin may have other repeating units to the extent that the properties of the present invention are not impaired.
  • the other repeating unit is preferably less than 50 mol%, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, or 5 mol% or less in all the repeating units.
  • the diol component used as a raw material of the formula (1) is mainly a diol component represented by the formula (a), and may be used alone or in combination of two or more.
  • R 1 , R 2 , L 1 , L 2 , m, n, j, and k are the same as the respective equations in the above equation (1).
  • R 1 and R 2 are hydrogen atoms
  • 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (hereinafter, also referred to as "BHEB”) or the like is used as the diol component of the formula (a). Can be mentioned.
  • the diol component of the formula (a) is 2,2'-bis (2-hydroxyethoxy) -3,3'-diphenyl-1,1'. -Binaphthalene, 2,2'-bis (2-hydroxyethoxy) -4,4'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -5,5'-diphenyl- 1,1'-Binaphthalene, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-Binaphthalene (hereinafter, also referred to as "BHEB-6P"), 2,2'- Bis (2-hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -8,8'-diphenyl-1,1'-binaphthalene, etc.
  • BHEB-6P 2,2'- Bis (2-hydroxyethoxy) -7
  • the diol component of the formula (a) is 2,2'-bis (2-hydroxyethoxy) -3,3'-di (1-naphthyl).
  • the diol component of the formula (a) is (a-3): 2,2'-bis (2-hydroxyethoxy) -6,6'-.
  • Di (2-thienyl) -1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -6,6'-di (3-thienyl) -1,1'-binaphthalene and the like can be mentioned.
  • the following formula (a-3): 2,2'-bis (2-hydroxyethoxy) -6,6'-di (2-thienyl) -1,1'-binaphthalene (hereinafter, "BHEB-4") , 6T ”) is preferable.
  • the diol component of the formula (a) is (a-4): 2,2'-bis (2-hydroxyethoxy) -4,4', 6,6'-Tetraphenyl-1,1'-binaphthalene (hereinafter, also referred to as "BHEB-4,6P”) and the like can be mentioned.
  • BHEB-4,6P 2,2'-bis (2-hydroxyethoxy) -4,4', 6,6'-Tetraphenyl-1,1'-binaphthalene
  • the diol component of the formula (a) is (a-5): 2,2'-bis (2-hydroxyethoxy) -4,4', 6,6'-tetra (2-naphthyl) -1,1'-binaphthalene (hereinafter, also referred to as "BHEB-4,6N”) and the like can be mentioned.
  • the diol component represented by the formula (a) BHEB, BHEB-6T, BHEB-6P, BHEB-6N, BHEB-4,6P, BHEB-4,6N are preferable, and BHEB-6P, BHEB-6N, BHEB. -4,6P and BHEB-4,6N are more preferable, and BHEB-6P, BHEB-6N and BHEB-4,6P are even more preferable.
  • the diol component used as a raw material of the formula (5) is mainly a diol component represented by the formula (c), and may be used alone or in combination of two or more.
  • the rings Z, R 1 , R 2 , Ar 1 , Ar 2 , L 1 , L 2 , j, k, m and n are the same as the respective formulas in the formula (5).
  • the diol component of the formula (b) is, for example, 9,9-bis (4- (2-hydroxyethoxy) phenyl) of the following formula (c-15). ) -2,7-Di (2-thienyl) fluorene can be mentioned.
  • the following formula (c-16) 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (hereinafter, also referred to as "BNEF”) ,
  • (c-18) 9,9-bis (6- (2-Hydroxyethoxy) -2-naphthyl) -2,7-di (2-naphthyl) fluorene can be mentioned.
  • Examples of the diol component represented by the formula (c) include BPEF, BOPPEF, BPDP2, BPDN1, BPDN2, and the above formula (c-15): 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2.
  • thermoplastic resin may be copolymerized with other diol components to the extent that the characteristics of the present invention are not impaired.
  • the other diol component is preferably less than 30 mol%, 20 mol% or less, 10 mol% or less, or 5 mol% or less in all repeating units.
  • thermoplastic resin examples include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and tricyclo [5.2.1.0 2,6.
  • Carbonated component of formula (1) or formula (5) As the carbonic acid component introduced as the unit represented by the formula (2) of the thermoplastic resin, a carbonic acid-forming derivative such as phosgene or carbonic acid diester is preferably used. Examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and bis (m-credyl) carbonate, and among them, diphenyl carbonate is preferable.
  • the dicarboxylic acid component used in the unit represented by the formula (1) or the formula (5) of the thermoplastic resin is mainly a dicarboxylic acid represented by HOOC-X-COOH or an ester-forming derivative thereof. Be done.
  • X represents a divalent linking group for giving a unit represented by the formula (1) or the formula (5).
  • a typical specific example of the dicarboxylic acid represented by the formula HOOC-X-COOH or an ester-forming derivative thereof is that the diols of the formulas (a) and (c) of the present invention form a dicarboxylic acid or an ester-forming derivative thereof. You can list what you are doing.
  • the dicarboxylic acid component used in the thermoplastic resin includes an aliphatic dicarboxylic acid component such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, and phthal.
  • an aliphatic dicarboxylic acid component such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, and phthal.
  • Monocyclic aromatic dicarboxylic acid components such as acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracendicarboxylic acid, phenanthrenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthalene (hereinafter, also referred to as "BCMB”), 9,9-bis (carboxy) Methyl) fluorene, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (1-carboxyethyl) fluorene, 9,9-bis (1-carboxypropyl) fluorene, 9,9-bis (2) -Carboxypropyl) fluorene
  • Examples include an acid component, a biphenyldicarboxylic acid component such as 2,2'-biphenyldicarboxylic acid, and an alicyclic dicarboxylic acid component such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalindicarboxylic acid, and isophthalic acid and terephthalic acid.
  • 2,6-naphthalenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthalene are preferable. These may be used alone or in combination of two or more types.
  • ester-forming derivative acid chloride or esters such as methyl ester, ethyl ester and phenyl ester may be used.
  • the thermoplastic resin of the present invention that is, a polycarbonate resin and a polyester carbonate resin and a polyester resin, reacts a carbonate precursor such as a carbonate diester with a reaction means known per se for producing ordinary resins, for example, in the case of polycarbonate, a dihydroxy compound. Manufactured by a method or the like.
  • the residual phenol content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 400 ppm, still more preferably 1 to 300 ppm.
  • the phenol content is preferably adjusted by the reaction time at a pressure of 1.3 kPa or less. If the reaction is not carried out at a degree of vacuum of 1.3 kPa or less, the phenol content is high. Further, if the reaction time is too long, it will be distilled off too much from the resin.
  • the phenol content may be adjusted after obtaining the thermoplastic resin.
  • a method of dissolving a thermoplastic resin in an organic solvent and washing the organic solvent layer with water a commonly used single-screw or twin-screw extruder, and a kneading device such as various kneaders, 133 to 13.3 Pa.
  • a method of volatilizing and removing at a pressure of 200 to 320 ° C. may be used.
  • the content of residual phenol is appropriate, the molding fluidity can be improved without impairing the heat resistance.
  • the thermal stability when the resin is heated and melted is improved, and mold contamination during resin injection molding can be prevented.
  • the thermoplastic resin preferably does not contain palladium.
  • the amount of residual palladium in the thermoplastic resin is preferably 10 ppm or less, more preferably 5.0 ppm or less, 3.0 ppm or less, 1.0 ppm or less, or 0.5 ppm, and 0.0 ppm or more, 0. .1 ppm or more, 0.2 ppm or more, or 0.5 ppm or more may be used.
  • coloring of the resin can be prevented.
  • the palladium compound is used as a catalyst when an aromatic substituent is bonded to a binaphthalene-based component unit or a fluorene-based component unit, and a binaphthalene-based component unit containing an aromatic substituent or an aromatic substituent is side-chained.
  • a thermoplastic resin containing a fluorene-based component unit contained in it usually remains.
  • the present inventors have found that the amount of residual palladium is related to the coloring of the thermoplastic resin.
  • a palladium removal treatment can be carried out by adding zeolite, activated carbon or the like to the monomer and / or the resin containing the palladium catalyst residue to adsorb the palladium catalyst residue.
  • the residual binaphthol content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 300 ppm, still more preferably 1 to 100 ppm, and particularly preferably 1 to 50 ppm. If the content of residual binaphthol in the thermoplastic resin is appropriate, coloring of the resin can be prevented.
  • the residual fluorenone content of the thermoplastic resin is preferably 1 to 500 ppm, more preferably 1 to 300 ppm, still more preferably 1 to 100 ppm, particularly preferably 1 to 50 ppm, still more preferably 1 to 30 ppm, and most preferably 1 to 1 to. It is 10 ppm. If the content of residual fluorenone in the thermoplastic resin is appropriate, coloring of the resin can be prevented.
  • the optical member of the present invention contains the above-mentioned thermoplastic resin.
  • Such an optical member is not particularly limited as long as it is an optical application in which the above-mentioned thermoplastic resin is useful, but is not limited to an optical fiber, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, and an optical film. , Substrate, optical filter, hard coat film and the like. Examples of the film include an optical film.
  • the optical member of the present invention may be composed of a resin composition containing the above-mentioned thermoplastic resin, and the resin composition may contain, if necessary, a heat stabilizer, a plasticizer, a light stabilizer, and the like. Additives such as polymerized metal inactivating agents, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, and mold release agents can be blended.
  • An image pickup lens can be mentioned as an optical member of the present invention. Examples of such an imaging lens include imaging lenses for mobile phones, smartphones, tablet terminals, personal computers, digital cameras, video cameras, in-vehicle cameras, surveillance cameras, and the like.
  • the imaging lens of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is particularly suitable.
  • the molding conditions for injection molding are not particularly limited, but the cylinder temperature of the molding machine is preferably 180 to 320 ° C, more preferably 220 to 300 ° C, and particularly preferably 240 to 280 ° C.
  • the mold temperature is preferably 70 to 130 ° C, more preferably 80 to 125 ° C, and particularly preferably 90 to 120 ° C.
  • the injection pressure is preferably 5 to 170 MPa, more preferably 50 to 160 MPa, and particularly preferably 100 to 150 MPa.
  • the solution was prepared by dissolving 10 mg of the obtained resin in 5 mL of chloroform.
  • the ratio of the peak area was calculated by the molecular weight in terms of polystyrene using GPC, and the ratio of the peak area having a number average molecular weight of less than 1,500 to the total peak area was converted into mass%.
  • the analysis was performed under the following measurement conditions.
  • Example 1 89.86 parts by mass of BHEB, 43.09 parts by mass of BNEF, 32.19 parts by mass of BCMB, 52.70 parts by mass of diphenyl carbonate (hereinafter, may be abbreviated as DPC), and tetrabutoxytitanium (IV).
  • DPC diphenyl carbonate
  • Example 1 shows the physical characteristics of the obtained polyester carbonate resin.
  • Examples 2 to 4 The composition of Examples 1 to 1 was changed as shown in Table 1 to obtain pellets of the polyester carbonate resins of Examples 2 to 4. Table 1 shows the physical characteristics of the obtained resin.
  • Comparative Examples 1 to 4 The resins obtained in Examples 1 to 4 were dissolved in dichloromethane at a concentration of 0.1 g / mL, and the resin was precipitated by dropping the resin in a large amount of acetone with stirring to prepare a sample in which oligomers were reduced. Table 1 shows the physical characteristics of the obtained resin. "result" Table 1 shows the evaluation results of Examples and Comparative Examples regarding the obtained resin. Further, the melt viscosities of Example 1 and Comparative Example 1 at 260 ° C. are shown in FIG.
  • thermoplastic resins of Examples 1 to 4 have a very high refractive index, and the fluidity is improved as compared with the case where the amount of oligomers having a number average molecular weight of less than 1,500 is less than 1.0% by mass. It was.
  • ⁇ Aspect II of the present invention> "Evaluation method" ⁇ Composition ratio> It was calculated by measuring the 1 H NMR spectrum of the obtained resin using JNM-ECZ400S / L1 manufactured by JEOL Ltd.
  • ⁇ Refractive index> 3 g of the obtained resin is dissolved in 50 ml of methylene chloride and cast on a glass petri dish. After sufficiently drying at room temperature, the film was dried at a temperature of 120 ° C.
  • BN-6Br 6,6'-dibromo-1,1'-bi-2-naphthol
  • a flask equipped with a stirrer, a cooler, and a thermometer 5 0.0 parts by mass, 2.3 parts by mass of ethylene carbonate, 0.16 parts by mass of potassium carbonate, and 15.0 parts by mass of toluene were charged and reacted at 110 ° C. for 5 hours.
  • the progress of the reaction was appropriately confirmed by HPLC, and it was confirmed that the peak area of BN-6Br with respect to the total peak area was 0.1% or less, and the reaction was terminated.
  • BHEB-6Br 2,2'-bis (2-hydroxyethoxy) -6,6'-dibromo-1,1'-binaphthalene
  • a white solid was obtained.
  • Activated carbon was added to the obtained organic layer and stirred for 1 hour to remove the palladium component, and then the activated carbon was filtered off and the organic layer was concentrated. After concentration, purification was performed by silica gel column chromatography to obtain white crystals of the desired product. When the amount of residual palladium was measured by ICP emission measurement, it was found to be 7 ppm in the case of BHEB-6P and 9 ppm in the case of BHEB-6N.
  • ⁇ Synthesis method B Synthesis of diols of formulas (a-1) and (a-2)> Formula (a-1) BHEB-6P and formula (a-2) BHEB-6N were synthesized by the synthesis method described in Synthesis Method A except that the palladium removal treatment was not performed. As a result, the desired gray crystal was obtained. When the amount of residual palladium was measured by ICP emission measurement, it was found to be 1210 ppm in the case of BHEB-6P and 1050 ppm in the case of BHEB-6N.
  • ⁇ Synthesis method C Synthesis of diol of formula (a-4)> Formula (a-4) BHEB-4,6P was synthesized by the synthesis method described below.
  • reaction solution was concentrated, dissolved in chloroform, a 1 M aqueous sodium hydroxide solution was added, and the mixture was washed with a separatory funnel. Then, washing with water was repeated until it became neutral. Next, activated carbon was added to the chloroform layer and stirred for 2 hours to remove the palladium component, and then the activated carbon was filtered off. Then, the organic layer was concentrated, hexane was added and recrystallized, and purification was performed by silica gel column chromatography to obtain white crystals of the desired product. When the amount of residual palladium was measured by ICP emission measurement, it contained 9 ppm.
  • ⁇ Synthesis method D Synthesis of diol of formula (a-4)> Formula (a-4) BHEB-4,6P was synthesized by the synthesis method described in Synthesis Method C except that the palladium removal treatment was not performed. As a result, the desired gray crystal was obtained. When the amount of residual palladium was measured by ICP emission measurement, it contained 812 ppm.
  • diols and dicarboxylic acids other than the above used in the following examples were commercially available products or manufactured by a known method.
  • Example 5 52.66 parts by mass of the synthesized BHEB-6P, 21.64 parts by mass of diphenyl carbonate (hereinafter, may be abbreviated as DPC), and 42.0 ⁇ 10-5 parts by mass of sodium hydrogen carbonate are stirred and distilled.
  • the jacket was heated to 180 ° C. to melt the raw material after placing it in the reaction vessel with the above and performing nitrogen substitution three times. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out.
  • the molar ratio of diol to DPC was 1: 1.01.
  • Example 11 31.6 parts by mass of BHEB-6P, 7.49 parts by mass of BHEB, 8.05 parts by mass of BCMB (2,2'-bis (carboxymethoxy) -1,1'-vinaphthalene), 13.5 parts by mass of DPC, and polymerization.
  • a catalyst 38.9 ⁇ 10 -3 parts by mass of aluminum acetylacetonate and 85.4 ⁇ 10 -3 parts by mass of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate with a stirrer and a distiller After putting it in the reaction vessel of No.
  • the jacket was heated to 180 ° C. to melt the raw materials. Then, the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, the pressure was reduced to 0.13 kPa over 70 minutes, and then the polymerization reaction was carried out under the conditions of 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets of polyester carbonate resin.
  • composition ratio of each diol component (BHEB-6P, BHEB), dicarboxylic acid (BCMB), and carbonic acid component (DPC) introduced into the polyester carbonate resin was determined by 1 H NMR measurement.
  • the characteristics of the obtained polyester carbonate resin are shown in Table 3.
  • Examples 12 to 18 and Comparative Examples 9 to 11 The charging ratio was changed so as to have the polymer composition shown in Table 3, and the polymerization catalysts of Examples 14 and 17 were changed to 1.70 ⁇ 10 -3 parts by mass of titanium tetrabutoxide. In the same manner, the polyester carbonate resins of Examples 12 to 18 and Comparative Examples 9 to 11 and the pellets of the polyester resins were obtained. "result" Table 2 shows the evaluation results of the polycarbonate resin. Table 3 shows the evaluation results of the polyester carbonate resin or the polyester resin.
  • thermoplastic resins of Examples 5 to 18 and Comparative Examples 5 to 11 Comparing the thermoplastic resins of Examples 5 to 18 and Comparative Examples 5 to 11, the b * value of each of the examples is 30 or less, which has an excellent hue for optical use, and further, for optical use so far. It was found that the refractive index of the polycarbonate resin made of BHEB, which had been used as the above, was significantly exceeded.

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Abstract

[Problème] Fournir une résine thermoplastique qui atteigne un équilibre entre un indice de réfraction élevé et une grande fluidité. [Solution] Une résine thermoplastique qui contient une unité de répétition représentée par la formule (1) et possède un indice de réfraction de 1,640-1,740 à une longueur d'onde de 589 nm. Formule (1) (Dans cette formule, R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène ou un groupe hydrocarboné en C1-14 qui peut comprendre un cycle aromatique; L1 et L2 représentent chacun indépendamment un groupe de liaison divalent; j et k représentent chacun indépendamment un nombre entier de 0 ou plus; m et n représentent chacun indépendamment 0 ou 1; W représente au moins un type choisi parmi le groupe représenté par la formule (2) ou la formule (3).) Formules (2) et (3) (Dans ces formules, X représente un groupe de liaison divalent.)
PCT/JP2020/026545 2019-07-19 2020-07-07 Résine thermoplastique et élément optique la contenant WO2021014962A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021261392A1 (fr) * 2020-06-26 2021-12-30 三菱瓦斯化学株式会社 Composition de résine
WO2022230471A1 (fr) * 2021-04-26 2022-11-03 三菱瓦斯化学株式会社 Composition de résine thermoplastique et ingrédient de formulation à ajouter à ladite composition de résine thermoplastique
WO2023085341A1 (fr) * 2021-11-12 2023-05-19 三菱瓦斯化学株式会社 Résine de carbonate de polyester, et lentille optique ainsi que film optique mettant en œuvre celle-ci
WO2023085339A1 (fr) * 2021-11-12 2023-05-19 三菱瓦斯化学株式会社 Résine thermoplastique, et lentille optique contenant celle-ci

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014185325A (ja) * 2013-02-20 2014-10-02 Teijin Ltd ポリカーボネート共重合体
WO2015170691A1 (fr) * 2014-05-07 2015-11-12 三菱瓦斯化学株式会社 Résine produite par polycondensation, et composition de résine
WO2017078071A1 (fr) * 2015-11-04 2017-05-11 三菱瓦斯化学株式会社 Procédé de production d'une composition de résine
JP2017088875A (ja) * 2015-11-04 2017-05-25 三菱瓦斯化学株式会社 樹脂組成物ならびにそれを含む光学レンズ、シートおよびフィルム
JP2017179323A (ja) * 2016-03-28 2017-10-05 大阪ガスケミカル株式会社 高屈折率ポリカーボネート系樹脂及び成形体
JP2018059074A (ja) * 2016-10-06 2018-04-12 大阪ガスケミカル株式会社 フルオレン骨格を有するポリエステル樹脂
WO2019044214A1 (fr) * 2017-08-30 2019-03-07 帝人株式会社 Résine thermoplastique et élément optique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9825102D0 (en) * 1998-11-16 1999-01-13 Insignia Solutions Plc Computer system
US6380352B1 (en) * 2000-08-29 2002-04-30 Eastman Chemical Company Polyester precursor purification process
JP5914261B2 (ja) * 2011-08-29 2016-05-11 大阪ガスケミカル株式会社 フルオレン骨格を有するポリエステル樹脂
JP6336261B2 (ja) * 2013-10-29 2018-06-06 帝人株式会社 熱可塑性樹脂およびそれらからなる光学部材
DE102015223559B3 (de) * 2015-11-27 2017-06-01 Schaeffler Technologies AG & Co. KG Kupplungsanordnung für ein Fahrzeug sowie Fahrzeug mit der Kupplungsanordnung

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014185325A (ja) * 2013-02-20 2014-10-02 Teijin Ltd ポリカーボネート共重合体
WO2015170691A1 (fr) * 2014-05-07 2015-11-12 三菱瓦斯化学株式会社 Résine produite par polycondensation, et composition de résine
WO2017078071A1 (fr) * 2015-11-04 2017-05-11 三菱瓦斯化学株式会社 Procédé de production d'une composition de résine
JP2017088875A (ja) * 2015-11-04 2017-05-25 三菱瓦斯化学株式会社 樹脂組成物ならびにそれを含む光学レンズ、シートおよびフィルム
JP2017179323A (ja) * 2016-03-28 2017-10-05 大阪ガスケミカル株式会社 高屈折率ポリカーボネート系樹脂及び成形体
JP2018059074A (ja) * 2016-10-06 2018-04-12 大阪ガスケミカル株式会社 フルオレン骨格を有するポリエステル樹脂
WO2019044214A1 (fr) * 2017-08-30 2019-03-07 帝人株式会社 Résine thermoplastique et élément optique

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021261392A1 (fr) * 2020-06-26 2021-12-30 三菱瓦斯化学株式会社 Composition de résine
CN115702214A (zh) * 2020-06-26 2023-02-14 三菱瓦斯化学株式会社 树脂组合物
EP4174126A4 (fr) * 2020-06-26 2023-11-15 Mitsubishi Gas Chemical Company, Inc. Composition de résine
CN115702214B (zh) * 2020-06-26 2024-02-20 三菱瓦斯化学株式会社 树脂组合物
WO2022230471A1 (fr) * 2021-04-26 2022-11-03 三菱瓦斯化学株式会社 Composition de résine thermoplastique et ingrédient de formulation à ajouter à ladite composition de résine thermoplastique
WO2023085341A1 (fr) * 2021-11-12 2023-05-19 三菱瓦斯化学株式会社 Résine de carbonate de polyester, et lentille optique ainsi que film optique mettant en œuvre celle-ci
WO2023085339A1 (fr) * 2021-11-12 2023-05-19 三菱瓦斯化学株式会社 Résine thermoplastique, et lentille optique contenant celle-ci

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