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
  • 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
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

• the present invention relates to a thermoplastic resin and an optical lens containing the same. More particularly, the present invention relates to polycarbonate resins and optical lenses 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 such as cameras, film-integrated cameras, and video cameras.
• Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems of high material cost, poor moldability, and low productivity.
• optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.
• Patent Documents 1 to 5 When optical resins are used as optical lenses, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, resistance to moist heat, etc. are required in addition to optical properties such as refractive index and Abbe number. Especially in recent years, there has been a demand for optical lenses having a high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 5).
• thermoplastic resins made from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene have excellent optical properties and are useful as various optical materials (Patent Document 6. ).
• Patent Document 6. thermoplastic resins made from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene have excellent optical properties and are useful as various optical materials.
• aberration correction is performed by combining multiple concave and convex lenses. That is, the chromatic aberration caused by the convex lens is synthetically canceled by combining the concave lens having the opposite sign of the chromatic aberration to that of the convex lens. At this time, the concave lens is required to have high dispersion (that is, low Abbe number).
• Patent Document 7 discloses that a copolymer of a bisphenol A-type polycarbonate structural unit and a structural unit represented by the following formula (E) has an improved refractive index.
• Examples of Patent Document 7 describe that a refractive index of 1.62 to 1.64 and an Abbe number of 23 to 26 were achieved. It is considered that the reason why the refractive index is improved in this way is due to the constitutional unit represented by the formula (E).
• Patent Document 8 discloses a copolymer of polycarbonate resin and bisphenol A containing structural units having a fluorene structure. Examples in this document describe achieving refractive indices of 1.616 to 1.636. Note that the structural unit disclosed in this document is different from the formula (E).
• An object of the present invention is to provide a thermoplastic resin that is excellent in optical properties such as refractive index, Abbe number, and haze, and is also excellent in in-plane birefringence, and an optical lens using the same.
• Another object of the present invention is to provide a polycarbonate resin having a high refractive index and a low Abbe number, a small absolute value of birefringence intensity, and a small in-plane birefringence, and an optical lens using the same.
• the present inventors have found that by blending a specific amount of a diol compound having a specific structure, optical properties such as refractive index, Abbe number and haze are excellent, and , and found that a thermoplastic resin having excellent in-plane birefringence can be obtained, and completed the present invention. Furthermore, the inventors have found that the above problems can be solved by the following polycarbonate resin and optical lens, and have completed the present invention.
• the present invention includes the following aspects. ⁇ 1> With respect to the total amount (100 mol%) of the structural units in the resin, 22 to 49 mol% of the structural unit (A) derived from the diol represented by the following general formula (1A) and the following general formula ( 40 to 75 mol% of the structural unit (B) derived from the diol represented by 2A), and 0 to 15 mol% of the structural unit (C) derived from the diol represented by the following general formula (3A), It is a thermoplastic resin containing (In general formula (1A), R a , R b , R aa and R bb are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, a substituent an alkoxy group having 1 to 20 carbon atoms which may have a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent; , an aryl group having 6 to 20 carbon atoms
• thermoplastic resin according to ⁇ 1> above is 0 to 8 mol % of the thermoplastic resin according to ⁇ 1> above.
• ⁇ 3> The thermoplastic resin according to ⁇ 1> or ⁇ 2> above, wherein the diol represented by the general formula (1) contains a diol represented by the following structural formula.
• ⁇ 4> The thermoplastic resin according to any one of ⁇ 1> to ⁇ 3> above, wherein the diol represented by the general formula (2A) contains at least one of the diols represented by the following structural formulas.
• ⁇ 5> The thermoplastic resin according to any one of ⁇ 1> to ⁇ 4> above, wherein the diol represented by the general formula (3A) contains a diol represented by the following structural formula.
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 5> which is a polycarbonate resin.
• thermoplastic resin according to any one of ⁇ 1> to ⁇ 6> further comprising a structural unit derived from at least one monomer selected from the following monomer group. .
• nD refractive index
• MVR melt volume flow rate
• An optical member comprising the thermoplastic resin according to any one of ⁇ 1> to ⁇ 14> above.
• An optical lens comprising the thermoplastic resin according to any one of ⁇ 1> to ⁇ 14>.
• An optical film comprising the thermoplastic resin according to any one of ⁇ 1> to ⁇ 14> above.
• the ratio of the structural unit represented by the following general formula (1B) is 1 mol% or more and less than 10 mol%
• the ratio of the structural unit represented by the following general formula (2B) is 10 to 60 mol%
• the above polycarbonate resin, wherein the ratio of structural units represented by the following general formula (3B) is 5 to 80 mol%.
• X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represents an integer of 1 to 10.
• Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represents an integer of 1 to 10.
• Z represents an alkylene group having 1 to 4 carbon atoms
• R 1 to R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms.
• thermoplastic resin excellent in optical properties such as refractive index, Abbe number, and haze, as well as excellent in-plane birefringence
• an optical lens containing the same Furthermore, according to the present invention, it is possible to provide a polycarbonate resin having a high refractive index and a low Abbe number, a small absolute value of birefringence intensity, and a small in-plane birefringence, and an optical lens containing the same. can.
• thermoplastic resin 22 to 49 mol% of a structural unit (A) derived from a diol represented by the following general formula (1A) with respect to the total amount (100 mol%) of structural units in the resin. and 40 to 75 mol% of the structural unit (B) derived from the diol represented by the following general formula (2A), and 0 of the structural unit (C) derived from the diol represented by the following general formula (3A). ⁇ 15 mol% of the thermoplastic resin.
• R a , R b , R aa and R bb each independently have a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), a substituent Alkyl groups having 1 to 20 carbon atoms (preferably alkyl groups having 1 to 6 carbon atoms), optionally substituted alkoxy groups having 1 to 20 carbon atoms (preferably having 1 to 6 carbon atoms) alkoxy group), an optionally substituted C5-20 cycloalkyl group (preferably a C5-10 cycloalkyl group), an optionally substituted C5-20 a cycloalkoxy group (preferably a cycloalkoxy group having 5 to 10 carbon atoms), an optionally substituted aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms
• R a and R b each independently represent a hydrogen atom, a methyl group, an ethyl group, or a phenyl group
• R aa and R bb each independently represent a hydrogen atom or a phenyl group.
• R h in -C ⁇ C-R h is an optionally substituted aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms), or O, N and S It represents an optionally substituted heteroaryl group having 6 to 20 carbon atoms (preferably a heteroaryl group having 6 to 12 carbon atoms) containing one or more hetero ring atoms selected from .
• Each X independently represents an optionally substituted alkylene group having 1 to 5 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, more preferably an ethylene group).
• a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, more preferably 1;
• substituents in the case of "optionally having a substituent" include halogen, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. be done.
• the structural unit (A) derived from the diol represented by the general formula (1A) is is preferable because the refractive index and the Abbe number are well balanced when used as an optical lens.
• BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
• OPPFL 9,9-bis[ 4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene
• R c and R d are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted carbon an alkoxy group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 5 to 20 carbon atoms, an optionally substituted cycloalkoxy group having 5 to 20 carbon atoms, and having a substituent an aryl group having 6 to 30 carbon atoms which may be substituted, a heteroaryl group having 6 to 30 carbon atoms which may be substituted, which contains one or more hetero ring atoms selected from O, N and S, a substituent selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms which may have R h is an optionally substituted aryl group having 6 to 20 carbon atoms, or an optionally
• R c and R d in the general formula (2A) are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms. group, more preferably an aryl group having 6 to 20 carbon atoms, still more preferably an aryl group having 6 to 14 carbon atoms. At least one of R c and R d in general formula (2A) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, particularly More preferably, two of R c and R d are aryl groups having 6 to 14 carbon atoms or 6 to 12 carbon atoms.
• R c and R d may be the same or different and are monocyclic or polycyclic aryl groups having 6 to 30 carbon atoms, or monocyclic or polycyclic aryl groups having 5 to 5 ring atoms. may be selected from 36 heteroaryl groups wherein 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen and the other ring atoms are carbon .
• the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may be unsubstituted.
• R c and R d may each be selected from the following group. i.e. azulenyl, which may be unsubstituted, phenyl and bonded to each other by a single bond, may be directly fused together, and/or saturated or unsaturated 4-10 membered monocyclic or bicyclic 2, 3, 4 or indenyl optionally substituted by 5 substituents, unsubstituted phenyl, phenyl substituted by one or two CN groups, phenyl and a 4- to 10-membered monocyclic or bicyclic hydrocarbon ring which may be bonded to each other by a single bond or may be directly fused together and/or saturated or unsaturated; substituted by 2, 3, 4 or 5 substituents selected from polycyclic aryl having 2, 3 or 4 phenyl rings optionally fused to Phenyl, which is may be directly fused to each other and/or may be fused to saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydro
• each of R c and R d may be selected from the following group. i.e. phenyl, which is unsubstituted or optionally substituted by 1, 2, 3, 4 or 5 phenyl groups, phenyl substituted by one or two CN groups, phenyl substituted by one or two polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl, and optionally further substituted by one phenyl group; unsubstituted or naphthyl substituted by one or two substituents selected from CN, phenyl and polycyclic aryl selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl; biphenylenyl, triphenylenyl, tetraphenylenyl, phenanthryl, pyrenyl, 9H-
• R c and R d are selected from the group consisting of phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl; preferable.
• each of R c and R d may be selected from the following group. i.e. a heteroaromatic monocyclic group having 5 or 6 ring atoms and having 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1 or 2 , or a heteroaromatic monocyclic group having 3 nitrogen atoms, or 1 sulfur atom and 0, 1, 2, or 3 nitrogen atoms, the other ring atoms being carbon atoms , a heteroaromatic polycyclic group comprising said monocyclic heteroaromatic ring and 1, 2, 3, 4 or 5 further aromatic rings selected from phenyl and monocyclic heteroaromatic rings; and the (hetero)aromatic rings of the polycyclic heteroaryl may be attached to each other by covalent bonds or may be directly fused to each other and/or saturated or unsaturated 4- to 10-membered rings a heteroaromatic polycyclic group optionally fused to a monocyclic or bicyclic hydrocarbon ring of at least one saturated or partially unsaturated 5- or
• each of R c and R d may be selected from the following group. i.e. furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuryl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furanyl, furo[2,3-b]furanyl, furo[3, 4-b]furanyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indoli
• Each X in the general formula (2A) is independently preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an ethylene group.
• c and d in the general formula (2A) are each independently preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and particularly preferably 2 or 3.
• the diol represented by the general formula (2A) preferably contains at least one of the diols represented by the following structural formulas.
• R e and R f are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), optionally having substituent(s) 1 to 20 alkyl group (preferably C1-C6 alkyl group), optionally substituted C1-C20 alkoxy group (preferably C1-C6 alkoxy group), substituent A cycloalkyl group having 5 to 20 carbon atoms (preferably a cycloalkyl group having 5 to 10 carbon atoms) which may have a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent (preferably , a cycloalkoxy group having 5 to 10 carbon atoms), an optionally substituted aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms), O
• R e and R f each independently represent a hydrogen atom or a phenyl group.
• R h in -C ⁇ C-R h is an optionally substituted aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms), or O, N and S It represents an optionally substituted heteroaryl group having 6 to 20 carbon atoms (preferably a heteroaryl group having 6 to 12 carbon atoms) containing one or more hetero ring atoms selected from .
• Each X independently represents an optionally substituted alkylene group having 1 to 5 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, more preferably an ethylene group).
• e and f each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, more preferably 1;
• the diol represented by the general formula (3A) is NOLE (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene represented by the following structural formula ) is particularly preferable, and in the present invention, a commercially available product or a synthesized product may be used.
• thermoplastic resin of one embodiment of the present invention is polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, etc., but is not particularly limited.
• a polyester resin or a polyester carbonate resin is preferable, and a polycarbonate resin is more preferable.
• the total ratio of structural units (A), (B) and (C) to all structural units is preferably 80 to 100 mol% of all structural units. , more preferably 90 to 100 mol %, particularly preferably 100 mol %. That is, the thermoplastic resin of one embodiment of the present invention, in addition to the structural units (A) to (C), is generally used as a structural unit of a polycarbonate resin or a polyester carbonate resin within a range that does not impair the effects of the present invention. Structural units derived from the aliphatic dihydroxy compound used and structural units derived from the aromatic dihydroxy compound can be included.
• various aliphatic dihydroxy compounds can be mentioned, and in particular, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 1,3-adamantanedimethanol, 2,2-bis( 4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl -5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc.
• aromatic dihydroxy compounds can be mentioned, but in particular 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 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, and bis(4-hydroxyphenyl) ketone, bisphenoxyethanol fluorene, and the like.
• bisphenol A 2,2-bis(4-hydroxyphenyl)propane
• 1,1-bis( 4-hydroxyphenyl)ethane 1,1-bis( 4-hydroxyphenyl)ethane
• the thermoplastic resin of one embodiment of the present invention also preferably contains structural units derived from at least one monomer selected from the following monomer group.
• R 1 and R 2 each independently represent a hydrogen atom, a methyl group or an ethyl group
• R 3 and R 4 each independently represent a hydrogen atom, a methyl group, an ethyl group or a represents an alkylene glycol of ⁇ 5.
• the polycarbonate resin of a preferred embodiment of the present invention contains alcohol-based compounds such as phenol-based compounds that may be produced as by-products during production, and diol components or carbonic acid diesters that remain unreacted as impurities.
• Alcoholic compounds such as phenolic compounds and carbonic acid diesters, which are impurities, can cause a decrease in strength and generation of odor when formed into a molded article.
• the content of the remaining phenolic compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 300 mass ppm or less based on 100 mass% of the polycarbonate resin.
• the content of the remaining diol component is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, and particularly preferably 10 mass ppm or less based on 100 mass% of the polycarbonate resin.
• the content of the remaining carbonic acid diester is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, and particularly preferably 10 mass ppm or less based on 100 mass% of the polycarbonate resin.
• it is preferable that the content of compounds such as phenol and t-butylphenol is small, and that the content of these compounds is within the above range.
• the content of the phenolic compound remaining in the polycarbonate resin can be measured by a method of analyzing the phenolic compound extracted from the polycarbonate resin using gas chromatography.
• the content of the alcohol-based compound remaining in the polycarbonate resin can also be measured by a method of analyzing the alcohol-based compound extracted from the polycarbonate resin using gas chromatography.
• the contents of diol components and carbonic acid diesters remaining in the polycarbonate resin can also be measured by extracting these compounds from the polycarbonate resin and analyzing them using gas chromatography.
• by-product alcoholic compounds such as phenolic compounds, diol components, and carbonic acid diesters may be reduced to the extent that they are not detected. good too. Moreover, if the amount is very small, the plasticity can be improved when the resin is melted.
• each of the remaining phenolic compound, diol component, or diester carbonate is, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more with respect to 100 mass% of the polycarbonate resin.
• the content of the remaining alcohol compound may be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more with respect to 100 mass% of the polycarbonate resin.
• by-product alcohol compounds such as phenolic compounds, diol components, and carbonic acid diesters in the polycarbonate resin are adjusted so as to fall within the above ranges by appropriately adjusting the polycondensation conditions and equipment settings. It is possible. It can also be adjusted by the conditions of the extrusion process after polycondensation.
• the residual amount of by-product alcoholic compounds such as phenolic compounds is related to the type of diester carbonate used in the polymerization of the polycarbonate resin, the polymerization reaction temperature, the polymerization pressure, and the like. By adjusting these, the residual amount of by-product alcoholic compounds such as phenolic compounds can be reduced.
• the content of the remaining by-product alcohol compound in the obtained polycarbonate resin is preferably 3000 mass ppm or less with respect to the polycarbonate resin (100 mass %).
• the content of the remaining alcohol-based compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 300 mass ppm or less based on 100 mass% of the polycarbonate resin.
• thermoplastic resin ⁇ Physical properties of thermoplastic resin> (1) Refractive index (nD)
• one of the characteristics of the thermoplastic resin is that it has a high refractive index. is more preferable, and 1.662 to 1.689 is particularly preferable.
• the refractive index can be measured by the method described in Examples below.
• the Abbe number of the thermoplastic resin is preferably 16.0 to 21.0, more preferably 16.3 to 20.5, and 16.6 to 20.2. is particularly preferred. In the present invention, the Abbe number can be measured by the method described in Examples below.
• one of the characteristics of the thermoplastic resin is high heat resistance, and the glass transition temperature (Tg) is preferably 130 to 190 ° C., and at 135 to 180 ° C. 140 to 165°C is particularly preferred.
• the glass transition temperature can be measured by the method described in Examples below.
• the polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 10,000 to 100,000, more preferably 20,000 to 70,000, 30,000 to 60,000 is particularly preferred.
• melt volume flow rate (MVR) of the thermoplastic resin is preferably 20-55, more preferably 25-50, particularly preferably 30-45.
• the melt volume flow rate (MVR) in the present invention can be measured by the method described in Examples below.
• the haze of the thermoplastic resin is preferably 0.01 to 1.00, more preferably 0.05 to 0.50, and 0.10 to 0.30 is particularly preferred. In the present invention, haze can be measured by the method described in Examples below.
• the in-plane birefringence of the thermoplastic resin is preferably 1 to 21, more preferably 2 to 15, and 2 to 13. It is particularly preferred to have In the present invention, the in-plane birefringence of the lens can be measured by the method described in Examples below.
• thermoplastic resin composition Another embodiment of the invention is a thermoplastic resin composition comprising the thermoplastic resin described above and an additive.
• the thermoplastic resin composition of the present embodiment is a thermoplastic resin other than the thermoplastic resin of the present invention containing the above-described structural units (A), (B) and (C) within a range that does not impair the desired effects of the present embodiment.
• a resin can be used in combination.
• Such resins include, but are not limited to, polycarbonate resins, polyester resins, polyester carbonate resins, (meth)acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, chloride At least one resin selected from the group consisting of vinyl resins, polyphenylene ether resins, polysulfone resins, polyacetal resins and methyl methacrylate-styrene copolymer resins can be used. Various known ones can be used as these, and they can be added to the thermoplastic resin composition singly or in combination of two or more.
• the thermoplastic resin composition preferably contains an antioxidant as the additive.
• an antioxidant it is preferable to contain at least one of a phenolic antioxidant and a phosphite antioxidant.
• phenolic antioxidants 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 e-2,4,6(1H,3H,5H)-trione, 4,4′,4′′-(1 -methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, ocladecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaery
• Phosphite antioxidants such as 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite, triisodecylphosphite, triphenylphosphite, 3,9-bis(octadecyloxy)-2,4,8,10- Tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphaspiro[5.5]undecane, 2,2′-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexylphosphite, tris(2,4-ditert-butylphenyl ) phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alky
• any one of the above may be used alone, or a mixture of two or more may be used. Further, in the present invention, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran- 2-ones may also be used.
• the antioxidant is preferably contained in an amount of 1 ppm to 3000 ppm by weight based on the total weight of the resin composition.
• the content of the antioxidant in the thermoplastic resin composition is more preferably 50 ppm to 2500 ppm by weight, more preferably 100 ppm to 2000 ppm by weight, and particularly preferably 150 ppm to 1500 ppm by weight. and more preferably 200 ppm to 1500 ppm by weight.
• the thermoplastic resin composition preferably contains a release agent as the additive.
• release agents include ester compounds such as 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, aliphatic polyhydric alcohols and aliphatic carboxylic acids. Full esters with acids, mono fatty acid esters, and the like can be mentioned.
• ester of an aliphatic polyhydric alcohol and an aliphatic carboxylic acid is used as the release agent, either a monoester, a full ester, or the like can be used.
• release agents include the following. Namely, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, sorbitan caprylate; Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; Higher alcohol fatty acid esters such as stearyl stearate; Glycerin monostearate, glycerin mono-12-hydroxystearate, etc.
• sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stea
• the release agent is preferably contained in an amount of 1 ppm to 5000 ppm by weight based on the total weight of the resin composition.
• the content of the release agent in the thermoplastic resin composition is more preferably 50 wt ppm to 4000 wt ppm, still more preferably 100 wt ppm to 3500 wt ppm, and particularly preferably 500 wt ppm to 13000 wt ppm. and more preferably 1000 ppm to 2500 ppm by weight.
• additives may be added to the thermoplastic resin composition 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, antifoaming agents, leveling agents, Examples include flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents.
• the content of additives other than antioxidants and release agents in the thermoplastic resin composition is preferably 10 wt ppm to 5.0 wt %, more preferably 100 wt ppm to 2.0 wt %. and more preferably 1000 ppm by weight to 1.0% by weight, but not limited thereto.
• the above additives may adversely affect the transmittance and should not be added in excess, eg the total amount added is within the above range.
• the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability after the completion of the polymerization reaction, but it is not always necessary to deactivate it. do not have.
• the known method for deactivating the catalyst by adding an acidic substance can be suitably carried out.
• acidic substances include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonate esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
• Phosphoric acid phosphoric acid, phosphoric acid such as phosphonic acid
• triphenyl phosphite monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di Phosphites such as n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite
• Phosphonic acid esters such as dioctyl and monooctyl phosphate
• Phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid
• Phosphonic acid esters such as diethyl phenylphosphonate
• deactivator From the viewpoint of the effect of the deactivator, the stability to the resin, and the like, p-toluene, butyl sulfonate, or tetrabutyl phosphonium dodecylbenzenesulfonate is particularly preferred.
• These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol, relative to the catalyst amount. If it is less than 0.01 times the molar amount of the catalyst, the deactivation effect becomes insufficient, which is not preferable. On the other hand, when the amount is more than 50 times the molar amount of the catalyst, the heat resistance of the resin is lowered, and the molded article tends to be colored, which is not preferable.
• the deactivator may be kneaded immediately after completion of the polymerization reaction, or may be kneaded after pelletizing the polymerized resin. In addition to the deactivator, other additives can also be added by the same method.
• thermoplastic resin or thermoplastic resin composition (hereinafter simply referred to as "resin composition") of the present invention can be suitably used for optical members.
• An embodiment of the present invention provides an optical member containing the resin composition of the present invention.
• optical members include optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, etc. It is not limited to these.
• the resin composition of the present invention has a high fluidity and can be molded by a casting method, so it is particularly suitable for manufacturing thin optical members.
• 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 member containing the resin composition of the present invention is produced by injection molding, it is preferable to perform molding under the conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, molding is carried out 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 color, and if it is lower than 260°C, the melt viscosity will be high and molding will be difficult. Moreover, when the mold temperature is higher than 170° C., it tends to be difficult to remove the molded piece made of the resin composition from the mold.
• 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, or the mold applied to the mold will not be sufficiently transferred. It is easy to become difficult.
• the resin composition can be suitably used for optical lenses.
• Optical lenses manufactured using the resin composition of the present invention have a high refractive index and excellent heat resistance, so conventionally, expensive high refractive index glass lenses have been used for telescopes, binoculars, television projectors, and the like. It can be used in various fields and is extremely useful.
• a lens molded from a resin containing a structural unit derived from any of the monomers of the above formulas can be superimposed and used as a lens unit.
• the optical lens of the present invention is preferably implemented in the form of an aspherical lens if necessary.
• Aspherical lenses can eliminate spherical aberration with a single lens, so there is no need to combine multiple spherical lenses to remove spherical aberration, which helps reduce weight and molding costs. be possible. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.
• the optical lens of the present invention is particularly useful as a material for thin, compact, and complicated-shaped optical lenses because of its high molding fluidity.
• the thickness of the central portion is preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, still more preferably 0.1 to 2.0 mm.
• the diameter is preferably 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, still more preferably 3.0 to 10.0 mm.
• the lens is a meniscus lens having a convex surface on one side and a concave surface on the other side.
• the optical lens of the present invention can be molded by any method such as mold molding, cutting, polishing, laser processing, electrical discharge machining, and etching. Among these, mold molding is more preferable from the viewpoint of manufacturing cost.
• the resin composition can be suitably used for optical films.
• the optical film produced using the polycarbonate resin of the present invention is excellent in transparency and heat resistance, and thus is suitably used for films for liquid crystal substrates, optical memory cards, and the like.
• the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.
• a second embodiment of the present invention comprises a structural unit represented by the following general formula (1B), a binaphthol derivative unit represented by the following general formula (2B), and a fluorene derivative represented by the following general formula (3B).
• X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represents an integer of 1 to 10.
• Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10.
• Z represents an alkylene group having 1 to 4 carbon atoms
• R 1 to R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms. group, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, e and f each independently represent an integer of 0 to 5; )
• the polycarbonate resin of the present invention preferably consists essentially of structural units represented by general formulas (1B) to (3B).
• "consisting essentially of” means that the polycarbonate resin of the present invention may contain other structural units within a range that does not impair the effects of the invention.
• the constituent units of the polycarbonate resin of the present invention preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more are composed of structural units represented by general formulas (1B) to (3B). .
• the proportion of the structural unit represented by the general formula (1B) is 1 mol% or more and less than 10 mol%, and the proportion of the structural unit represented by the general formula (2B) is 10 to 60 mol. %, and the proportion of the structural unit represented by the general formula (3B) is 5 to 80 mol %.
• the ratio of the structural unit represented by general formula (1B) is 2 to 9 mol%, and the general formula ( The ratio of the structural unit represented by 2B) is 20 to 60 mol%, and the ratio of the structural unit represented by general formula (3B) is preferably 30 to 70 mol%.
• the proportion of the structural unit represented by the general formula (2B) is 3 to 8 mol%, the proportion of the structural unit represented by the general formula (2B) is 30 to 60 mol%, and the proportion of the structural unit represented by the general formula (3B) A proportion of 40 to 60 mol % is particularly preferred.
• the polycarbonate resin of the present invention is not particularly limited in how the structural units represented by general formulas (1B) to (3B) are included in the resin.
• the polycarbonate resin may contain a copolymer containing structural units represented by general formulas (1B) to (3B), and a ternary containing a homopolymer consisting of each structural unit It may be a system resin. Alternatively, it may be a blend of a copolymer containing structural units represented by general formulas (1B) and (2B) and a homopolymer containing structural units represented by general formula (3B). A copolymer containing structural units represented by formulas (1B) and (2B) and a copolymer containing structural units represented by general formulas (1B) and (3B) may be blended. .
• the polycarbonate resin of the present invention may contain any of random, block and alternating copolymer structures.
• the preferred polystyrene equivalent weight average molecular weight (Mw) of the polycarbonate resin of the present invention is 20,000 to 200,000. More preferably, the polystyrene equivalent weight average molecular weight (Mw) is 25,000 to 120,000, still more preferably 28,000 to 55,000, and particularly preferably 30,000 to 45,000.
• Mw is less than 20,000, the compact becomes brittle, which is not preferable. If Mw is more than 200,000, the melt viscosity becomes high, making it difficult to take out the resin after production.
• the refractive index (nD) of the polycarbonate resin of the present invention at 23° C. and a wavelength of 589 nm is preferably 1.635 to 1.695, more preferably 1.640 to 1.690, and still more preferably 1.645 to 1.685. and particularly preferably 1.650 to 1.680.
• the polycarbonate resin of the present invention has a high refractive index (nD) and is suitable for optical lens materials.
• the refractive index can be measured by the method of JIS B 7071-2:2018 using an Abbe refractometer for a film having a thickness of 0.1 mm.
• the Abbe number ( ⁇ ) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, still more preferably 21 or less.
• the melt volume flow rate (MVR) of the polycarbonate resin of the present invention is preferably 10-100, more preferably 30-100, and particularly preferably 30-50.
• MVR can be measured by the method described in Examples below.
• the birefringence intensity of the polycarbonate resin of the present invention is preferably ⁇ 0.6 to +0.7, more preferably ⁇ 0.5 to +0.5, and particularly preferably ⁇ 0.3 to +0.3. be.
• the birefringence intensity can be measured by the method described in Examples below.
• the in-plane birefringence of the polycarbonate resin of the present invention is preferably 0.1-15, more preferably 1-10, and particularly preferably 2-7.
• the in-plane birefringence of the lens can be measured by the method described in Examples below.
• the haze of the polycarbonate resin of the present invention is preferably 0.05 to 3.00, more preferably 0.10 to 2.00.
• haze can be measured by the method described in Examples below.
• the polycarbonate resin of the present invention can be blended with other resins and used for the production of molded articles.
• other resins include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate and the like.
• antioxidants can be added to the polycarbonate resin of the present invention.
• molding methods include, but are not limited to, injection molding, compression molding, cast molding, roll processing, extrusion molding, and stretching.
• the glass transition temperature (Tg) is preferably 90 to 180°C, more preferably 95 to 175°C, still more preferably 100 to 170°C, still more preferably 130 to 170°C, particularly preferably 135 to 150°C. If the Tg is lower than 90°C, the usable temperature range becomes narrow, which is not preferable. On the other hand, if it exceeds 180° C., the melting temperature of the resin becomes high, and the resin tends to be decomposed or colored, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the glass transition temperature of the resin becomes large with a general-purpose mold temperature controller.
• the lower limit of Tg is preferably 130°C, more preferably 135°C, and the upper limit of Tg is preferably 160°C, more preferably 150°C.
• the amount of residual phenol contained in the polycarbonate resin of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 50 ppm or less.
• the amount of residual diphenyl carbonate (DPC) contained in the polycarbonate resin of the present invention is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
• Polycarbonate resins having structural units represented by general formulas (1B) to (3B) according to the present invention are represented by general formulas (4B) to (6B) below.
• X represents an alkylene group having 1 to 4 carbon atoms
• a and b each independently represents an integer of 1 to 10.
• Y represents an alkylene group having 1 to 4 carbon atoms
• c and d each independently represent an integer of 1 to 10.
• Z represents an alkylene group having 1 to 4 carbon atoms
• R 1 to R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms.
• a compound represented by as the dihydroxy component can be prepared by using a compound represented by as the dihydroxy component and reacting it with a carbonate precursor such as a carbonate diester.
• a carbonate precursor such as a carbonate diester.
• the compound represented by the general formulas (4B) to (6B) and a carbonate precursor such as a diester carbonate are mixed in the presence or absence of a mixed catalyst consisting of a basic compound catalyst or an ester exchange catalyst or both. It can be produced by a melt polycondensation method in the presence of a catalyst.
• Compounds of general formula (4B) include 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes.
• compounds of general formula (4) include 9,9-bis[6-(1-hydroxymethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2 -yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphthalen-2-yl]fluorene, and 9,9-bis[6-(4-hydroxybutoxy)naphthalen-2-yl]fluorene, etc. is mentioned. Among them, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene is preferred. These may be used alone or in combination of two or more.
• a compound in which either a or b is 0 may be produced as an impurity by-product.
• the total content of such impurities in the monomer containing the compound of general formula (4B) as a main component is preferably 1000 ppm or less, more preferably 500 ppm or less, and 200 ppm or less. More preferably, it is particularly preferably 100 ppm or less.
• fluorenone which is one of the raw materials, may also be included as an impurity.
• the content of fluorenone is preferably 1000 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, and 10 ppm or less in the monomer containing the compound of general formula (4B) as a main component. is particularly preferred. Fluorenone contained in the monomer containing the compound of general formula (4B) as a main component may remain in the resin after polymerization. The smaller the content of fluoronolene, the better the hue of the resin, which is preferable.
• the total amount of compounds in which a and b in general formula (4B) are not the same is 50 ppm or less in the monomer containing the compound of general formula (4B) as a main component. is preferred, and 20 ppm or less is more preferred.
• the compound of general formula (4B) can be produced by various synthetic methods. For example, as described in Japanese Patent No. 5442800, (a) a method of reacting fluorenones and hydroxynaphthalenes in the presence of hydrogen chloride gas and mercaptocarboxylic acid, (b) acid catalyst (and alkyl mercaptan) (c) a method of reacting a fluorenone with a hydroxynaphthalene in the presence of hydrochloric acid and a thiol (mercaptocarboxylic acid, etc.); (d) a method of reacting a fluorenone with a hydroxynaphthalene in the presence of sulfuric acid and A method of producing bisnaphtholfluorene by reacting fluorenones and hydroxynaphthalenes in the presence of thiols (mercaptocarboxylic acids, etc.) and crystallizing them with a crystallization solvent composed of hydrocarbons and a polar solvent, etc
• 9,9-bis(hydroxynaphthyl)fluorenes which are then reacted with compounds corresponding to [XO]a and [XO]b groups (such as alkylene oxides and haloalkanols).
• compounds corresponding to [XO]a and [XO]b groups such as alkylene oxides and haloalkanols.
• 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene is obtained by reacting 9,9-bis[6-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.
• dihydroxy compounds represented by general formula (5B) examples include 2,2′-bis(1-hydroxymethoxy)-1,1′-binaphthalene, 2,2′-bis(2-hydroxyethoxy)-1, 1'-binaphthalene, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthalene, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene and the like.
• BHEBN 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene
• BHEBN 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene
• a compound in which either c or d is 0 may be produced as an impurity by-product.
• the total content of such impurities in the monomer containing the compound of general formula (5B) as a main component is preferably 1000 ppm or less, more preferably 500 ppm or less, and 200 ppm or less. More preferably, it is particularly preferably 100 ppm or less.
• the total amount of compounds in the general formula (5B) where c and d are not the same (i.e., c ⁇ d) is 50 ppm or less in the monomer containing the compound of the general formula (5B) as a main component. is preferred, and 20 ppm or less is more preferred.
• Examples of dihydroxy compounds represented by general formula (6B) include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as “BPEF”), 9,9-bis [4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-( 2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)- 3-phenylphenyl]fluorene (hereinafter sometimes abbreviated as “BPPEF”) and the like.
• BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
• BPPEF 9,9-bis[4-(
• 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene are preferred. These may be used alone or in combination of two or more.
• a compound in which either e or f is 0 may be produced as an impurity by-product.
• the total content of such impurities in the monomer containing the compound of general formula (6B) as a main component is preferably 1000 ppm or less, more preferably 500 ppm or less, and 200 ppm or less. More preferably, it is particularly preferably 100 ppm or less.
• the total amount of compounds in which e and f in general formula (6B) are not the same that is, e ⁇ f) is 50 ppm or less in the monomer containing the compound of general formula (6B) as a main component. is preferred, and 20 ppm or less is more preferred.
• aromatic dihydroxy compounds examples include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, and bisphenol.
• P, bisphenol PH, bisphenol TMC, bisphenol Z and the like are exemplified.
• Carbonic acid diesters used in the present invention include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like.
• diphenyl carbonate is particularly preferred.
• Diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 mol, more preferably in a ratio of 0.98 to 1.10 mol, per 1 mol of the total dihydroxy compound.
• examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• alkali metal compounds used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals.
• alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metal compounds.
• magnesium hydroxide, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like are used.
• nitrogen-containing compounds include quaternary ammonium hydroxides and salts thereof, amines, and the like.
• quaternary ammonium hydroxides having an alkyl group, an aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; 2-methylimidazole, 2-phenylimidazole, benzimidazole or imidazoles such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabut
• Salts of zinc, tin, zirconium, lead, etc. are preferably used as transesterification catalysts, and these can be used alone or in combination.
• transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin acetate (II), tin acetate (IV), and dibutyltin.
• Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV) and the like are used.
• These catalysts are used in a ratio of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 3 mol, preferably in a ratio of 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mol, per 1 mol of the total dihydroxy compound. .
• melt polycondensation is performed under heat and under normal or reduced pressure while removing by-products through transesterification.
• Melt polycondensation in this composition system is performed by melting the compounds represented by the general formulas (4B) to (6B) and the diester carbonate in a reaction vessel, and then allowing the by-product monohydroxy compound to stay in the reaction vessel. It is desirable to The pressure can be controlled by closing the reaction apparatus, depressurizing or pressurizing the reaction apparatus for retention.
• the reaction time for this step is 20 minutes or more and 240 minutes or less, preferably 40 minutes or more and 180 minutes or less, and particularly preferably 60 minutes or more and 150 minutes or less.
• the by-produced monohydroxy compound is distilled off immediately after its formation, the finally obtained polycarbonate resin has a low content of high molecular weight substances.
• the finally obtained polycarbonate resin has a large content of high molecular weight substances.
• the melt polycondensation reaction may be performed continuously or batchwise.
• the reactor used for the reaction may be of a vertical type equipped with anchor-type stirring blades, MAXBLEND stirring blades, helical ribbon-type stirring blades, etc., or a horizontal type equipped with paddle blades, lattice blades, spectacle blades, etc. It may be of the extruder type equipped with a screw.
• the catalyst may be removed or deactivated after completion of the polymerization reaction in order to maintain thermal stability and hydrolytic stability.
• a method of deactivating the catalyst by adding a known acidic substance can be preferably carried out.
• acidic substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonate esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
• Phosphoric acid phosphoric acid, phosphoric acid such as phosphonic acid
• triphenyl phosphite monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di Phosphites such as n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite
• Phosphonic acid esters such as dioctyl and monooctyl phosphate
• Phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid
• Phosphonic acid esters such as diethyl phenylphosphonate
• butyl p-toluenesulfonate and tetrabutylphosphonium dodecylbenzenesulfonate are particularly preferably used.
• These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol, relative to the catalyst amount. If it is less than 0.01 times the molar amount of the catalyst, the deactivation effect becomes insufficient, which is not preferable. On the other hand, when the amount is more than 50 times the molar amount of the catalyst, the heat resistance of the resin is lowered, and the molded article tends to be colored, which is not preferable.
• a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C may be provided.
• a horizontal apparatus equipped with stirring blades with excellent surface renewal performance such as paddle blades, lattice blades, or spectacle blades, or a thin film evaporator is preferably used.
• the polycarbonate resin of the present invention is desired to contain as little foreign matter as possible, and filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably carried out.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
• filtration of the resulting resin through a polymer filter is preferably carried out.
• the mesh of the polymer filter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
• the step of collecting resin pellets must naturally be in a low dust environment, preferably class 6 or less, more preferably class 5 or less.
• a copolymer containing structural units represented by the general formulas (1B) to (3B) may be produced, and the compounds represented by the general formulas (4B) to (6B) are separately polymerized to obtain each It may be produced as a ternary resin containing a homopolymer consisting of constitutional units.
• a copolymer containing structural units represented by general formulas (1B) and (2B) and a homopolymer containing structural units represented by general formula (3B) may be blended after polymerization.
• a copolymer containing structural units represented by (1B) and (2B) and a copolymer containing structural units represented by general formulas (1B) and (3B) may be polymerized and then blended.
• An optical molded article can be produced using the polycarbonate resin of the present invention.
• it is molded by any method such as injection molding, compression molding, extrusion molding, or solution casting. Since the polycarbonate resin of the present invention is excellent in moldability and heat resistance, it can be used particularly advantageously in optical lenses that require injection molding.
• the polycarbonate resin of the present invention can be used by mixing with other resins such as other polycarbonate resins and polyester resins.
• Antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylene Bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester,
• processing stabilizers include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers.
• Phosphorous processing heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.
• triphenylphosphite tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite
• Sulfur-based processing heat stabilizers include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate). , dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and the like.
• the content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight per 100 parts by weight of the polycarbonate resin.
• esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or full esters of polyhydric alcohols and fatty acids.
• ester of monohydric alcohol and fatty acid an ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms is preferable.
• Partial or full esters of a polyhydric alcohol and a fatty acid are preferably partial or full esters of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
• esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate.
• Partial or full esters of polyhydric alcohols with saturated fatty acids include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol
• Full esters or partial esters of pentaerythritol and the like can be mentioned.
• the content of these releasing agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and 0.02 to 0.02 parts by weight, based on 100 parts by weight of the polycarbonate resin. A range of 0.5 parts by weight is more preferred.
• At least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
• Absorbents are preferred. That is, any of the ultraviolet absorbers listed below may be used alone, or two or more thereof may be used in combination.
• Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1,1 ,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy -5-tert-octylpheny
• Benzophenone UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2- methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.
• Triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol and the like.
• Cyclic imino ester UV absorbers include 2,2′-bis(3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis(3,1-benzoxazin-4-one). , 2,2′-m-phenylenebis(3,1-benzoxazin-4-one), 2,2′-(4,4′-diphenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2′-(1,5-naphthalene)bis(3,1-benzoxazin-4-one) ), 2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2-nitro-p-phenylene)bis(3,1- benzoxazin-4-one) and 2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).
• cyanoacrylate ultraviolet absorber 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenyl acryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like.
• the content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and still more preferably 0 parts by weight with respect to 100 parts by weight of the polycarbonate resin. 0.05 to 0.8 parts by weight. Within such a blending amount range, it is possible to impart sufficient weather resistance to the polycarbonate resin depending on the application.
• the polycarbonate resin of the present invention has a high refractive index and a low Abbe number.
• a coat layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical molded body, if necessary.
• the antireflection layer may be a single layer or multiple layers, and may be organic or inorganic, but is preferably inorganic. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride are exemplified.
• the optical lens manufactured using the polycarbonate resin of the present invention has a high refractive index, a low Abbe number, a small absolute value of birefringence intensity, and a small in-plane birefringence. It can be used in fields such as projectors where expensive high-refractive-index glass lenses have conventionally been used, and is extremely useful. If necessary, it is preferably used in the form of an aspherical lens. Since aspherical lenses can eliminate spherical aberration with a single lens, there is no need to remove spherical aberration by combining multiple spherical lenses, which helps reduce weight and production costs. be possible. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.
• the optical lens is molded by any method such as injection molding, compression molding, injection compression molding, and the like. According to the present invention, it is possible to easily obtain a high-refractive-index, low-birefringence aspherical lens, which is technically difficult to process with a glass lens.
• the molding environment In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.
• Optical films produced using the polycarbonate resin of the present invention are excellent in transparency and heat resistance, and are therefore suitably used for films for liquid crystal substrates, optical memory cards, and the like.
• the molding environment In order to avoid foreign matter from entering the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.
• refractive index (nD) Based on JIS B 7071-2: 2018, polycarbonate resin was molded to obtain a V block and used as a test piece. The refractive index was measured at 23° C. using a refractometer (KPR-3000 manufactured by Shimadzu Corporation).
• Tg Glass transition temperature Measurement was performed with a differential thermal scanning calorimeter in accordance with JIS K7121-1987 with a heating program of 10°C/min. Differential scanning calorimeter: X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.
• Example 2A-4A Comparative Examples 1A-8A
• a polycarbonate resin was obtained in the same manner as in Example 1A, except that the raw materials shown in Table 1 were used.
• Table 2 shows the physical properties of the obtained resin.
• Example 2B Comparative Examples 1B to 3B
• a polycarbonate resin was obtained in the same manner as in Example 1B, except that the raw materials shown in Table 4 were used.
• Table 3 shows the physical properties of the obtained resin.

Landscapes

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

Priority Applications (5)

Applications Claiming Priority (4)

Publications (1)

Family

ID=86335770

Family Applications (1)

Country Status (6)

Cited By (1)

Citations (14)

• 2022
  • 2022-11-09 TW TW111142787A patent/TW202328276A/zh unknown
  • 2022-11-10 JP JP2023559879A patent/JPWO2023085339A1/ja active Pending
  • 2022-11-10 US US18/707,773 patent/US20250092193A1/en active Pending
  • 2022-11-10 EP EP22892837.0A patent/EP4431545A4/en active Pending
  • 2022-11-10 KR KR1020247009358A patent/KR20240095171A/ko active Pending
  • 2022-11-10 WO PCT/JP2022/041824 patent/WO2023085339A1/ja not_active Ceased

Patent Citations (14)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events