Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses

Definitions

• the present invention relates to a thermoplastic resin and an optical lens containing the same. More specifically, the present invention relates to 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 the material for the optical lenses used in the optical systems of various cameras, including cameras with built-in film and video cameras.
• Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material costs, poor moldability, and low productivity.
• optical lenses made from optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.
• optical resins are used as optical lenses, in addition to optical properties such as refractive index and Abbe number, they are required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and moist heat resistance.
• Patent Documents 1 to 5 there has been a demand for optical lenses with high refractive index and high heat resistance, and various resins have been developed.
• the objective of the present invention is to provide a thermoplastic resin that has excellent optical properties, such as refractive index, Abbe number, and photoelastic coefficient, as well as excellent heat resistance, and an optical lens using the same.
• thermoplastic resins that have excellent optical properties, such as refractive index, Abbe number, and photoelastic coefficient, as well as excellent heat resistance, and thus completed the present invention.
• thermoplastic resin including a structural unit (A) derived from a monomer represented by the following formula (1): ⁇ 2> The thermoplastic resin according to ⁇ 1> above, wherein the monomer represented by formula (1) is a monomer represented by formula (5): ⁇ 3> The thermoplastic resin according to ⁇ 1> or ⁇ 2> above, wherein the thermoplastic resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin.
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 3> above, wherein 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):
• R a and R b are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, 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 cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring
• R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, 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 cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent;
• Y 1 is a single bond, a fluorene group which may have a substituent, or any one of the structural formulae represented by the following formulae (8) to (14), (In formulas (8) to (15), R 61 , R 62 , R 71 , R 72 , R 81 and R 82 each independently represent a hydrogen atom, a halogen atom, an alkyl
• 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 of 0 to 4; a and b each independently represent an integer of 0 to 10.
• a and B each independently represent an alkylene group having 2 or 3 carbon atoms.
• the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, DPBHBNA, BPM, and BCFL.
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 6> above, further comprising a structural unit derived from at least one monomer selected from the following monomer group: (In the above formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms, and i and ii each independently represent an integer of 1 to 3.) ⁇ 8> The thermoplastic resin according to any one of ⁇ 1> to ⁇ 7> above, wherein the thermoplastic resin has a weight average molecular weight (Mw) in terms of polystyrene of 10,000 to 100,000.
• Mw weight average molecular weight
• ⁇ 11> The thermoplastic resin according to any one of ⁇ 1> to ⁇ 10> above, wherein the thermoplastic resin has a glass transition temperature of 135 to 160° C.
• An optical lens comprising the thermoplastic resin according to any one of ⁇ 1> to ⁇ 14> above.
• the present invention can provide a thermoplastic resin that has excellent optical properties, such as refractive index, Abbe number, and photoelastic coefficient, as well as excellent heat resistance, and an optical lens that contains the same.
• thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following formula (1).
• the monomer represented by formula (1) is a monomer represented by formula (5) below.
• the monomer represented by formula (1) may be a commercially available product, or may be prepared by the method described in Japanese Patent No. 3673574.
• the thermoplastic resin in one embodiment of the present invention is not particularly limited and may be a polyester resin, a polycarbonate resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, a polymethacrylic acid ester resin, or the like. However, it is preferably a polycarbonate resin, a polyester carbonate resin, or a polyester resin, and more preferably contains a structural unit (A) represented by the following formula:
• the proportion of the structural unit (A) represented by the above formula in all structural units is not particularly limited, but is preferably 1 to 80 mol %, more preferably 1 to 60 mol %, and particularly preferably 5 to 50 mol %. In another embodiment of the present invention, the proportion of the structural unit (A) represented by the above formula in all structural units is preferably 30 to 80 mol %, more preferably 40 to 80 mol %, and particularly preferably 50 to 70 mol %.
• thermoplastic resin of one embodiment of the present invention can contain, in addition to the structural unit (A) represented by the above formula, a structural unit derived from an aliphatic dihydroxy compound or a structural unit derived from an aromatic dihydroxy compound that is generally used as a structural unit of a polycarbonate resin or a polyester carbonate resin.
• various aliphatic dihydroxy compounds may be mentioned, including 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, and 1,6-hexanediol.
• aromatic dihydroxy compounds include various compounds, particularly 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, and the like.
• bisphenol A 2,2-bis(4-hydroxyphenyl)propane
• bis(4-hydroxyphenyl)methane 1,1-bis(4-hydroxyphenyl)ethane
• the thermoplastic resin according to one embodiment of the present invention preferably contains a structural unit (B) derived from a monomer represented by the following general formula (6).
• R a and R b are each independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, 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 cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and which contains one or more heterocyclic atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -
• R h represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and which contains one or more heterocyclic atoms selected from O, N, and S.
• R a and R b are preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, 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, or an aryl group having 6 to 12 carbon atoms which may have 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 and has a total of 12 to 20 carbon atoms.
• a and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms.
• m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.
• a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.
• thermoplastic resin according to one embodiment of the present invention preferably has a structural unit (C) derived from a monomer represented by the following general formula (7).
• R c and R d are each independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, 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 cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent.
• Rc and Rd are preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, 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, or an aryl group having 6 to 12 carbon atoms which may have a substituent.
• Y 1 is a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (15), and is preferably a single bond or a structural formula represented by the following formula (8).
• R 61 , R 62 , R 71 , R 72 , R 81 and R 82 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R 61 and R 62 , or R 71 and R 72 bond together to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent.
• r and s each independently represent an integer of 0 to 5,000.
• a and B are each independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms.
• p and q are each independently an integer from 0 to 4, and preferably 0 or 1.
• a and b are each independently an integer from 0 to 10, and preferably an integer from 0 to 5, and more preferably an integer from 0 to 2, for example, 0 or 1.
• structural unit (C) examples include BCFL (9,9-bis(4-hydroxy-3-methylphenyl)fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), BNEF (9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M (BPM), bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclohexyl)phenyl, and bis
• the thermoplastic resin according to one embodiment of the present invention may contain a structural unit derived from a monomer represented by the following general formula (1).
• Each L 1 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 of 0 to 4;
• t represents an integer of 0 or 1.
• thermoplastic resin essentially contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not containing the structural unit (C), a polymer containing the structural unit (C) but not containing the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing the structural unit (B) and a polymer containing the structural unit (C), or a combination thereof.
• Examples of the polymer containing the structural unit (C) but not containing the structural unit (B) include those having structural units of the following formulae (I-1) to (I-3), and examples of the copolymer having the structural unit (B) and the structural unit (C) include those having structural units of the following formulae (II-1) to (II-4).
• m and n each represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1;
• the number of repeating units of formula (I-3) is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably 1.
• the polymer having multiple types of constitutional units either a block copolymer in which the values of m and n are large, for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values of m and n are 1 is used.
• m and n each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.
• a block copolymer in which the values of m and n are large for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values of m and n are 1 is used.
• the molar ratio of the structural unit (B) to the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.
• 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, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.
• thermoplastic resin according to one embodiment of the present invention preferably further contains a structural unit derived from at least one monomer selected from the following monomer group: (In the above formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms, and i and ii each independently represent an integer of 1 to 3.)
• impurities such as alcohol-based compounds such as phenol-based compounds that may be generated as by-products during production, and diol components or carbonate diesters that remain unreacted may be present.
• Impurities such as alcohol compounds such as phenol compounds and carbonic acid diesters can cause a decrease in strength and odor when molded into a molded article, so it is preferable that the content of these compounds is as small as possible.
• the content of the residual phenolic compounds is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, based on 100% by mass of the polycarbonate resin.
• the content of the remaining diol component is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the polycarbonate resin.
• the content of the remaining carbonate diester is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by 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 in which the phenolic compound extracted from the polycarbonate resin is analyzed by gas chromatography.
• the content of the alcohol-based compound remaining in the polycarbonate resin can also be measured by a method in which the alcohol-based compound extracted from the polycarbonate resin is analyzed by gas chromatography.
• the contents of the diol component and the carbonate diester remaining in the polycarbonate resin can also be measured by a method in which these compounds are extracted from the polycarbonate resin and analyzed by gas chromatography.
• the content of by-produced alcohol compounds such as phenolic compounds, diol components and carbonate diesters may be reduced to the point where they are not detectable, but from the viewpoint of productivity, they may be present in small amounts as long as they do not impair the effect. Also, small amounts can improve the plasticity of the resin when it is melted.
• each of the remaining phenolic compounds, diol components, or carbonate diesters may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin.
• the content of the remaining alcohol-based compound may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more relative to 100% by mass of the polycarbonate resin.
• the content of by-produced alcohol compounds such as phenolic compounds, diol components and carbonate diesters in the polycarbonate resin can be adjusted to fall within the above range by appropriately adjusting the polycondensation conditions and the settings of the equipment. It can also be adjusted by the conditions of the extrusion process after polycondensation.
• the amount of by-product alcohol compounds such as phenolic compounds remaining is related to the type of carbonic acid diester used in the polymerization of polycarbonate resin, the polymerization reaction temperature, the polymerization pressure, etc. By adjusting these factors, the amount of by-product alcohol compounds such as phenolic compounds remaining can be reduced.
• the content of by-produced alcohol compounds remaining in the obtained polycarbonate resin is 3000 ppm by mass or less relative to the polycarbonate resin (100% by mass).
• the content of the remaining alcohol compounds is preferably 3000 ppm by mass or less, more preferably 1000 ppm by mass or less, and particularly preferably 300 ppm by mass or less relative to 100% by mass of the polycarbonate resin.
• thermoplastic resin ⁇ Physical properties of thermoplastic resin> (1) Refractive index (nD)
• one of the features of the thermoplastic resin is that it has a high refractive index, and the refractive index is preferably 1.500 to 1.700, more preferably 1.550 to 1.700, and particularly preferably 1.580 to 1.650.
• the refractive index is also preferably 1.560 to 1.610.
• the refractive index can be measured by the method described in the examples below.
• the Abbe number of the thermoplastic resin is preferably 22.0 to 35.0, more preferably 22.0 to 33.0, even more preferably 23.0 to 32.0, and particularly preferably 23.0 to 30.0. In another embodiment of the present invention, the Abbe number is also preferably 25.0 to 33.2. 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 high heat resistance, and the glass transition temperature (Tg) is preferably 135 to 160 ° C, more preferably 140 to 160 ° C, even more preferably 142 to 158 ° C, and particularly preferably 144 to 155 ° C.
• the glass transition temperature (Tg) is preferably 110 to 210 ° C, more preferably 130 to 200 ° C, even more preferably 140 to 180 ° C, and particularly preferably 145 to 160 ° C.
• the glass transition temperature can be measured by the method described in the examples below.
• the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 10,000 to 60,000.
• one of the features of the thermoplastic resin is that it has a low photoelastic coefficient, and the photoelastic coefficient is preferably 25 to 45, more preferably 25 to 38, and particularly preferably 28 to 38.
• the photoelastic coefficient can be measured by the method described in the examples below.
• the water absorption of the thermoplastic resin is preferably 0.10 to 0.50%, and more preferably 0.20 to 0.45%.
• the water absorption can be measured by the method described in the examples below.
• the dimensional change rate upon water absorption of the thermoplastic resin is preferably close to 0%, for example, preferably -0.1 to 0.10%, and more preferably -0.01 to 0.05%.
• the dimensional change rate upon water absorption can be measured by the method described in the examples described later.
• thermoplastic resin composition containing the above-mentioned thermoplastic resin and an additive.
• the thermoplastic resin composition of this embodiment does not impair the desired effect of this embodiment.
• resins other than the thermoplastic resin of the present invention containing the structural unit (A) can be used in combination.
• Such resins are not particularly limited, but examples thereof include polycarbonate resins, polyester resins, polyester carbonates, etc.
• Resin (meth)acrylic resin, polyamide resin, polystyrene resin, cycloolefin resin, acrylonitrile-butadiene-styrene copolymer resin, vinyl chloride resin, polyphenylene ether resin, polysulfone resin, polyacetal resin, and methyl methacrylate-styrene copolymer resin.
• various known resins can be used, and one type can be added alone or two or more types can be added in combination to the thermoplastic resin composition.
• the thermoplastic resin composition preferably contains an antioxidant as the additive.
• an antioxidant it is preferable to contain at least one of a phenol-based antioxidant and a phosphite-based antioxidant.
• Phenolic antioxidants include 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-triazine-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'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentane
• phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 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-ethylhexyl phosphite, Examples of the phosphite include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)
• the antioxidant is preferably contained in an amount of 1 ppm by weight 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 ppm by weight to 2500 ppm by weight, even more preferably 100 ppm by weight to 2000 ppm by weight, particularly preferably 150 ppm by weight to 1500 ppm by weight, and even more preferably 200 ppm by weight to 1200 ppm by weight.
• the thermoplastic resin composition preferably contains a release agent as the additive.
• the release agent include ester compounds, for example, glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, full esters or mono fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids, etc.
• ester compounds for example, glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, full esters or mono fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids, etc.
• ester compounds for example, glycerin fatty acid esters such
• sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and 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
• Glycerol fatty acid ester monoglycerides including: glycerol monohydroxystearates such as glycerol monostearate and glycerol mono 12-hydroxystearate, monoglycerides such as glycerol
• the release agent is preferably contained in an amount of 1 ppm by weight to 5000 ppm by weight based on the total weight of the resin composition.
• the content of the release agent in the thermoplastic resin composition is more preferably 50 ppm by weight to 4000 ppm by weight, even more preferably 100 ppm by weight to 3500 ppm by weight, particularly preferably 500 ppm by weight to 13000 ppm by weight, and even more preferably 1000 ppm by weight to 2500 ppm by weight.
• the thermoplastic resin composition may contain other additives in addition to the antioxidant and release agent described above.
• additives that may be contained in the thermoplastic resin composition include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents.
• the content of the additives other than the antioxidant and the mold release agent in the thermoplastic resin composition is preferably 10 ppm by weight to 5.0% by weight, more preferably 100 ppm by weight to 2.0% by weight, and even more preferably 1000 ppm by weight to 1.0% by weight, but is not limited thereto.
• the above-mentioned additives may adversely affect the transmittance, and therefore it is preferable not to add them in excess, and for example, the total amount added is within the above-mentioned range.
• thermoplastic resin or thermoplastic 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.
• the optical member includes, but is not limited to, an optical disk, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a base, an optical filter, a hard coat film, and the like.
• the resin composition of the present invention is suitable for producing thin optical members in particular because it can be molded by a casting method with high flow.
• the optical member produced using the resin composition of the present invention may be an optical lens.
• the optical member produced using the resin composition of the present invention may be an optical film.
• an optical component containing the resin composition of the present invention is manufactured by injection molding, it is preferable to perform molding under conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, molding is performed under conditions of a cylinder temperature of 270 to 320°C and a mold temperature of 100 to 160°C. If the cylinder temperature is higher than 350°C, the resin composition will decompose and discolor, and if it is lower than 260°C, the melt viscosity will be high and molding will be difficult. Also, if the mold temperature is higher than 170°C, it will be difficult to remove a molded piece made of the resin composition from the mold. On the other hand, if the mold temperature is less than 90°C, the resin will harden too quickly in the mold during molding, making it difficult to control the shape of the molded piece, and it will be difficult to fully transfer the shape of the molded piece.
• the resin composition can be suitably used for optical lenses.
• the optical lenses produced using the resin composition of the present invention have a high refractive index and excellent heat resistance, and are therefore extremely useful in fields where expensive high refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors.
• R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group
• R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.
• a lens molded from a resin containing a structural unit derived from any one of the monomers of the above formulas can be superimposed and used as a lens unit.
• the optical lens of the present invention is preferably implemented as an aspherical lens if necessary.
• Aspherical lenses can reduce spherical aberration to essentially zero with a single lens, making it unnecessary to remove spherical aberration by combining multiple spherical lenses, which allows for weight reduction and reduced molding costs.
• aspherical lenses are particularly useful as camera lenses, among other optical lenses.
• the optical lens of the present invention has high molding fluidity and is therefore particularly useful as a material for optical lenses that are thin, small, and have complex shapes.
• Specific lens sizes are preferably 0.05 to 3.0 mm thick at the center, more preferably 0.05 to 2.0 mm, and even more preferably 0.1 to 2.0 mm thick.
• the diameter is preferably 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm.
• the lens is preferably a meniscus lens with one convex side and the other concave side.
• the optical lens of the present invention can be formed by any method such as metal molding, cutting, polishing, laser processing, electric discharge processing, etching, etc. Among these, metal molding is more preferable in terms of production costs.
• the resin composition can be suitably used for optical films.
• optical films produced using the polycarbonate resin of the present invention are excellent in transparency and heat resistance, and therefore are suitably used for liquid crystal substrate films, optical memory cards, etc.
• the molding environment In order to prevent contamination of the optical film with foreign matter as much as possible, the molding environment must of course be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.
• Weight average molecular weight The weight average molecular weight of the obtained resin was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene.
• GPC device Tosoh Corporation, HLC-8420GPC
• Detector RI detector
• Standard polystyrene Standard polystyrene kit PStQuick C, manufactured by Tosoh Corporation Sample solution: 0.2% by mass tetrahydrofuran solution
• Eluent tetrahydrofuran
• Eluent flow rate 0.6 mL/min
• Refractive Index (nD) A polycarbonate resin was molded into a V-block to prepare a test piece according to JIS B 7071-2:2018. The refractive index was measured at 23°C using a refractometer (Shimadzu Corporation KPR-3000).
• the obtained resin was dissolved in dichloromethane to obtain a resin solution.
• the resin solution was spread on a tray, and the solvent was evaporated to obtain a film having a thickness of 0.1 mm, which was used as a sample piece.
• the photoelastic coefficient was measured by an ellipsometer. Measurement method: The photoelastic coefficient was calculated by measuring the change in birefringence with respect to the change in load at a wavelength of 633 nm.
• Ellipsometer JASCO Corporation Ellipsometer M-220
• Water absorption rate (%) (Mt-M0)/M0 ⁇ 100 The mass was measured in an environment controlled at 23° C. ⁇ 2° C. (21° C. to 25° C.).
• Example 1-1 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) 16.694g (0.0381 mol), 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2-cyclohexyl-5-methylphenol] (Bis3M6C-M) 8.7912g (0.0163 mol), diphenyl carbonate (DPC) 12.000g (0.0560 mol) and 2.5 ⁇ 10 -2 mol/L sodium bicarbonate aqueous solution 20 ⁇ l (5.0 ⁇ 10 -7 mol) were placed in a 300mL reactor equipped with a stirrer and a distillation device, and the system was replaced with nitrogen.
• BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
• Bis3M6C-M 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2-cyclohexyl-5-methylphenol
• the reactor was immersed in an oil bath heated to 200 ° C to start the transesterification reaction.
• the temperature was raised to 240° C. over 140 minutes, and the pressure was reduced to 0.1 kPa or less, and after maintaining this for 30 minutes, nitrogen gas was introduced into the reaction system to return the pressure to 101.3 kPa, thereby obtaining a polycarbonate resin.
• the physical properties of the obtained resin are shown in Table 1.
• Example 1 A polycarbonate resin was obtained in the same manner as in Example 1-1, except that the dihydroxy compound (diol) in the raw material was one shown in Table 1. The physical properties of the obtained resin are shown in Table 1.
• Example 2-7 Comparative Example 2
• a polycarbonate resin was obtained in the same manner as in Example 2-1, except that the dihydroxy compound (diol) in the raw material was one shown in Table 2.
• the physical properties of the obtained resin are shown in Table 2.
• Example 3-1 As raw materials, 8543.3 g (19.5 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 4500.0 g (8.4 mol) of 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2-cyclohexyl-5-methylphenol] (Bis3M6C-M), 6142.5 g (28.7 mol) of diphenyl carbonate (DPC), and 5.5 ml (5.5 x 10 -4 mol) of a 1.0 x 10 -1 mol/L aqueous sodium hydrogen carbonate solution were added to a 50-L reactor equipped with a stirrer and a distillation device.
• BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
• 4500.0 g 8.4 mol) of 4,4'-[1,3-phenylenebis(1-methylethylidene)
• the reaction system was then replaced with nitrogen, and heated to 180°C over 30 minutes under a nitrogen atmosphere of 760 Torr and stirred. After the raw materials were completely dissolved, the temperature was raised to 190° C. over 20 minutes, and then the degree of vacuum was adjusted to 200 Torr. The temperature was kept at 190° C. and 200 Torr for 20 minutes to carry out an ester exchange reaction. The temperature was further raised to 220° C. at a rate of 30° C./hr, and the degree of vacuum was adjusted to 150 Torr. Thereafter, the temperature was raised to 240°C at a rate of 60°C/hr, and the degree of reduced pressure was adjusted to 100 Torr.
• the pressure was then reduced to 1 Torr or less over 40 minutes, and a polymerization reaction was carried out for 30 minutes with stirring under conditions of 240°C and 1 Torr. After the reaction was completed, nitrogen was introduced into the reactor, pressure was applied, and the produced polycarbonate resin was pelletized with a pelletizer and withdrawn.
• the obtained polycarbonate resin pellets were dried at 100°C for 3 hours, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Adekastab AO-60; manufactured by ADEKA CORPORATION) was added to the polycarbonate resin at 1000 ppm, and glycerin monostearate (stearic acid monoglyceride, S-100A; manufactured by Riken Vitamin Co., Ltd.) was added to the polycarbonate resin at 1000 ppm, followed by kneading with a twin-screw extruder.
• the physical properties of the obtained resin are shown in Table 3. The details of the extrusion are as follows. Twin screw extruder: IPEC Corporation IPT-35 Resin temperature: 260°C Discharge speed: 20kg/h Screw rotation speed: 200 rpm
• Example 3 (Examples 3-2 to 3-6, Comparative Example 3) A polycarbonate resin was obtained in the same manner as in Example 3-1, except that the dihydroxy compound (diol) in the raw material was one shown in Table 3. The physical properties of the obtained resin are shown in Table 3.
• a system containing 30 mol % or more of Bis3M6-M is preferred because it has a low water absorption rate and a low rate of dimensional change due to water absorption.
• a system containing more than 50 mol % Bis3M6C-M, particularly 70/30, is preferred because it has low water absorption and low dimensional change due to water absorption.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Polyesters Or Polycarbonates (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91588725

Family Applications (1)

Country Status (7)

Citations (10)

• 2023
  • 2023-12-20 KR KR1020257015266A patent/KR20250123766A/ko active Pending
  • 2023-12-20 JP JP2024566098A patent/JPWO2024135717A1/ja active Pending
  • 2023-12-20 US US19/135,543 patent/US20260085150A1/en active Pending
  • 2023-12-20 EP EP23907077.4A patent/EP4640740A1/en active Pending
  • 2023-12-20 TW TW112149691A patent/TW202440727A/zh unknown
  • 2023-12-20 WO PCT/JP2023/045642 patent/WO2024135717A1/ja not_active Ceased
  • 2023-12-20 CN CN202380084443.0A patent/CN120322482A/zh active Pending

Patent Citations (11)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events