Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
  • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
  • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/19—Hydroxy compounds containing aromatic rings
  • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
  • C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/64—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
  • C08G63/78—Preparation processes
• • 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
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • 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
  • C08G64/307—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

Definitions

• the present invention relates to a method for producing a thermoplastic resin, a thermoplastic resin obtained by the method, 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 method for producing a thermoplastic resin that has excellent reactivity and excellent color.
• thermoplastic resin with excellent reactivity and excellent color can be obtained, which led to the completion of the present invention.
• thermoplastic resin having a structural unit (A) represented by the following formula includes a step of reacting a crystal of a dicarboxylate diester represented by the following formula (a) which satisfies at least one of the following: (i) a maximum melting endotherm temperature of 177 to 181° C.
• thermoplastic resin is a polyester resin or a polyester carbonate resin.
• thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (b) and/or a structural unit (C) derived from a monomer represented by the following general formula (c):
• 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
• 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 (1) to (7), (In formulas (1) to (7), R 61 , R 62 , R 71 and R 72 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be
• 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 from 0 to 10.
• ⁇ 5> The production method according to any one of ⁇ 1> to ⁇ 4> above, wherein a catalyst containing an alkali metal or an alkaline earth metal is used.
• ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5> above, wherein the catalyst is present in an amount of 0.1 to 10 ppm relative to the thermoplastic resin.
• thermoplastic resin has a weight average molecular weight (Mw) in terms of polystyrene of 10,000 to 100,000.
• Mw weight average molecular weight
• thermoplastic resin has a YI of 0.1 to 14.
• thermoplastic resin according to ⁇ 9> or ⁇ 10> above wherein the thermoplastic resin is a polyester resin or a polyester carbonate resin.
• thermoplastic resin is a polyester resin or a polyester carbonate resin.
• An optical member comprising the thermoplastic resin according to any one of ⁇ 9> to ⁇ 11> above.
• An optical lens comprising the thermoplastic resin according to any one of ⁇ 9> to ⁇ 11> above.
• An optical film comprising the thermoplastic resin according to any one of ⁇ 9> to ⁇ 11> above.
• a method for producing a thermoplastic resin having excellent reactivity and excellent color can be provided.
• the crystals of the dicarboxylate diester represented by the above formula (a) when one having a melting endothermic maximum temperature of 177 to 181°C in the above ⁇ 1> or one having a powder X-ray diffraction pattern in the above ⁇ 1> is used, the bulk density of the dicarboxylate diester, which is one of the raw materials of the thermoplastic resin, increases, which is advantageous in that it is easy to handle when it is put into a reaction vessel.
• the polymerization activity is improved and the amount of catalyst added can be reduced, which makes it easier to obtain a resin with excellent color tone.
• thermoplastic resin having a structural unit (A) represented by the following formula, the method comprising a step of reacting a crystal of a dicarboxylate diester represented by the following formula (a) which satisfies at least one of the following: (i) a maximum melting endotherm temperature of 177 to 181° C.
• the present inventors have found that the crystals of the dicarboxylic acid diester (phenyl ester) represented by the above formula (a) have higher reactivity than similar methyl esters or carboxylic acids, and that the polymerization reaction proceeds with less catalyst. In addition, it has been found that the color of the obtained thermoplastic resin is excellent, possibly due to the high thermal stability of the phenyl ester itself.
• the crystals of the dicarboxylate diester represented by the formula (a) can be produced by a specific production method described below, and have a melting point (maximum melting endotherm temperature by differential scanning calorimetry) of 177 to 181° C.
• the method for producing the crystals of the dicarboxylate diester represented by the above formula (a) will be described in detail below.
• Crystals of dicarboxylic acid diester represented by formula (a) The crystals of the dicarboxylate diester represented by the above formula (a) can be prepared by reacting a compound represented by the following general formula (2):
• R 1a and R 1b each independently represent an optionally branched alkyl group having 1 to 6 carbon atoms.
• reaction step with diphenyl carbonate or phenyl acetate (reaction step), and a step of crystallizing the dicarboxylate represented by formula (a) using at least one organic compound selected from the group consisting of aromatic hydrocarbons, alcohols, ethers and esters as a crystallization solvent (crystallization step).
• the reaction step will be described in detail below.
• the alkyl group having 1 to 6 carbon atoms in R 1a and R 1b of the above general formula (2) may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
• the compound represented by the above general formula (2) may be purified by a conventional method (for example, the crystals described in JP 2021-017406 A), or may be unpurified (for example, the compound of the above general formula (2) contained in the reaction mixture obtained by reacting 1,1'-bi-2-naphthol with a halogenated acetate).
• the dicarboxylic acid diester represented by formula (a) has low solubility in general organic solvents such as aromatic hydrocarbons, even if an unpurified compound represented by the above general formula (2) is used as a raw material, impurities contained in the previous process can be easily removed by crystallization after the reaction.
• Examples of the organic titanium compounds include alkoxy titanium catalysts.
• Examples of the alkoxy titanium catalysts include the tetramethyl ester, tetra-n-propyl ester, tetraisopropyl ester, tetra-n-butyl ester, tetraisobutyl ester, tetra-tert-butyl ester, tetra-2-ethylhexyl ester, tetraoctyl ester, tetraphenyl ester, tetrabenzyl ester, and tetratolyl ester of titanic acid. These organic titanium compounds may be used alone or in combination of two or more.
• the amount of the organotitanium compound used is, for example, 0.025 to 0.10 moles per mole of the compound represented by the above general formula (2).
• the amount of diphenyl carbonate or phenyl acetate used is, for example, 4 to 25 moles per mole of the compound represented by the above general formula (2).
• the reaction of the compound represented by the above general formula (2) with diphenyl carbonate or phenyl acetate may be carried out using diphenyl carbonate or phenyl acetate as a solvent, or may be carried out in the presence of an organic solvent other than diphenyl carbonate or phenyl acetate.
• organic solvent include aromatic hydrocarbons.
• aromatic hydrocarbons include toluene, xylene, and mesitylene.
• the amount used is, for example, 0.05 to 5.0 parts by weight per part by weight of the compound represented by the above general formula (2).
• These other organic solvents may be used alone, or two or more of them may be used in combination.
• the reaction of the compound represented by the above general formula (2) with diphenyl carbonate or phenyl acetate can be carried out, for example, at 130 to 170°C. If necessary, the reaction may be carried out under normal pressure or reduced pressure while removing by-products. When the reaction is carried out under reduced pressure, the internal pressure is, for example, 0.67 to 6.7 kPa.
• the resulting reaction mixture can be subjected to a crystallization step to obtain crystals of the dicarboxylic acid diester represented by the above formula (a).
• the reaction mixture obtained after carrying out the reaction step may be subjected to post-treatment such as neutralization and washing with water, or concentration, etc., as necessary.
• the crystallization step will be described in detail below.
• the solvent (crystallization solvent) used in the crystallization step is at least one organic compound selected from the group consisting of aromatic hydrocarbons, alcohols, ethers, and esters.
• aromatic hydrocarbons include toluene, xylene, and mesitylene.
• alcohols include alcohols having 1 to 6 carbon atoms, which may have a branch, such as methanol, ethanol, propanol, butanol, pentanol, and hexanol.
• ethers include diethyl ether, tetrahydrofuran, and cyclopentyl methyl ether.
• esters include ethyl acetate, propyl acetate, and butyl acetate.
• crystallization solvents aromatic hydrocarbons are preferred.
• aromatic hydrocarbons are preferred.
• These crystallization solvents may be used alone or in combination of two or more types, but it is preferable to use them alone from the viewpoints of reducing environmental impact and costs, since the solvent can be recycled more easily if used alone.
• the amount of the crystallization solvent used is, for example, 1 to 10 parts by weight per part by weight of the dicarboxylic acid diester represented by the above formula (a).
• the amount of the dicarboxylic acid diester represented by the above formula (a) contained in the reaction mixture can be measured, for example, by the absolute calibration curve method or the internal standard method using liquid chromatography.
• a method for crystallizing the dicarboxylic acid diester represented by the above formula (a) includes, for example, dissolving the dicarboxylic acid diester represented by the above formula (a) in a crystallization solvent, cooling the resulting solution to precipitate crystals, and filtering off the precipitated crystals.
• the temperature at which the dicarboxylic acid diester represented by the above formula (a) is dissolved in the crystallization solvent is, for example, from the boiling point of the solvent used to 115°C.
• the temperature at which the resulting solution is cooled to precipitate crystals is, for example, 80 to 100°C.
• the dicarboxylic acid diester represented by the above formula (a) can be crystallized without using seed crystals, and therefore, unlike 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl, it is not necessary to go through the above-mentioned complicated steps to precipitate crystals, and crystallization can be easily performed.
• the cooling rate is, for example, 0.1 to 20°C/min, and the cooling end temperature is, for example, 0 to 25°C.
• the crystals can then be extracted by standard methods such as filtration and centrifugation.
• the extracted crystals usually contain a solvent, but the solvent can be removed by drying. Drying can be performed, for example, by heating under normal pressure or reduced pressure.
• the heating temperature is, for example, 70 to 90°C.
• the crystals of the dicarboxylic acid diester represented by the above formula (a) thus obtained can be further purified by recrystallization, distillation, adsorption, column chromatography, etc.
• thermoplastic resin of the present invention is a method for producing a polyester carbonate resin
• a dicarboxylic acid or an ester-forming derivative thereof other than the crystal of the dicarboxylic acid diester represented by the above formula (a) can be used in combination in an amount of up to 30 mol %.
• the dicarboxylic acid or an ester-forming derivative thereof used in the step of obtaining an intermediate product can be any dicarboxylic acid or an ester-forming derivative thereof known for producing an intermediate product commonly used in this field.
• Dicarboxylic acids include, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, monocyclic aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(2-carboxyethy
• ester-forming derivative acid chlorides of the above carboxylic acids, and esters such as methyl esters, ethyl esters, and phenyl esters may be used.
• a dicarboxylic acid for example, a compound represented by the following general formula (C) is also preferably used.
• R1 and R2 each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms
• n and m each independently represent an integer of 0 or greater
• R3 to R10 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 20 carbon atoms.
• dicarboxylic acid represented by formula (C) or its ester-forming derivatives are shown below, but the invention is not limited thereto.
• thermoplastic resin comprising a structural unit (A) derived from a crystal of a dicarboxylate diester represented by the following formula (a), which has a melting endothermic maximum temperature of 177 to 181° C. as measured by differential scanning calorimetry:
• the crystals of the dicarboxylate diester represented by the above formula (a) have a melting point (maximum melting endotherm temperature by differential scanning calorimetry) of 177 to 181°C.
• a melting point maximum melting endotherm temperature by differential scanning calorimetry
• thermoplastic resin in one embodiment of the present invention is preferably a polyester carbonate resin or a polyester resin, although there are no particular limitations on the type, such as polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, etc.
• 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 %, of all structural units.
• the 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
• 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 (b).
• 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 carbon number of 12 to 20.
• 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.
• structural unit (B) examples include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.
• 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 (c).
• 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 (1) to (7), and is preferably a single bond or a structural formula represented by the following formula (1).
• R 61 , R 62 , R 71 and R 72 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 BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol Bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclododecylidenebisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexyliden
• 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-2) and 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, n, and l 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 (or m, n and l) are large, for example, 100 or more, or a random copolymer can be used.
• a random copolymer is preferred, and more preferably a random copolymer in which the values of m and n (or m, n and l) are 1 is used.
• the molar ratio of the structural unit (B) 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, and 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.)
• the thermoplastic resin according to one embodiment of the present invention preferably contains a structural unit (D) derived from a monomer represented by the following general formula (16).
• the content of the structural unit (D) derived from the monomer represented by general formula (16) is preferably 1 to 50 mol %, and more preferably 1 to 30 mol %, of all structural units.
• 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.
• each L 1 independently represents a divalent linking group.
• L 1 is preferably an alkylene group having 1 to 12 carbon atoms, which may have a substituent, more preferably an alkylene group having 1 to 5 carbon atoms, even more preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an ethylene group.
• Examples of the substituent of the alkylene group of L 1 include an alkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, and combinations thereof, and specific examples of these groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, a methoxy group, and an ethoxy group.
• R 3 and R 4 when present, each independently represent a halogen atom or a substituent having 1 to 20 carbon atoms which may contain an aromatic group.
• the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
• substituent having 1 to 20 carbon atoms which may contain an aromatic group include a methyl group, a phenyl group, a naphthyl group, a thienyl group, and a benzothienyl group.
• the naphthyl group include a 1-naphthyl group and a 2-naphthyl group.
• Examples of the thienyl group include a 2-thienyl group and a 3-thienyl group.
• examples of the benzothienyl group include a 2-benzo[b]thienyl group and a 3-benzo[b]thienyl group. These groups may further have a substituent, and examples of such a substituent include, but are not limited to, those described above as the substituent of the alkylene group of L 1 .
• j3 and j4 each independently represent an integer of 0 to 4.
• j3 and j4 are preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
• t represents an integer of 0 or 1, and is preferably 1.
• the monomer represented by the general formula (16) preferably has a structure represented by the following formula (16').
• the polyester carbonate resin of the preferred embodiment of the present invention can be produced by melt polycondensation using the crystals of the dicarboxylic acid diester constituting the above-mentioned structural unit (A), a diol compound, and a carbonic acid diester as raw materials.
• the diol compound can be an aliphatic dihydroxy compound or an aromatic dihydroxy compound as mentioned above, and preferably a monomer represented by the above-mentioned general formula (b) and/or a monomer represented by the above-mentioned general formula (c).
• the polyester carbonate resin can be produced in the presence of a basic compound catalyst, an ester exchange catalyst, or a mixed catalyst consisting of both of them as a polycondensation catalyst.
• Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate.
• diphenyl carbonate is particularly preferred from the viewpoint of reactivity and purity.
• the amount of carbonic acid diester added can be determined by assuming that the diol component and the dicarboxylic acid component react in equimolar amounts, and the remainder reacts with the carbonic acid diester.
• the carbonic acid diester is preferably used in a ratio of 0.60 to 1.50 moles per mole difference between the diol component and the dicarboxylic acid component, more preferably 0.80 to 1.40 moles, even more preferably 1.00 to 1.30 moles, even more preferably 1.00 to 1.25 moles, and particularly preferably 1.00 to 1.20 moles.
• the molecular weight of the polyester carbonate resin can be controlled.
• Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. From the viewpoints of catalytic effect, price, distribution volume, effect on the color of the resin, etc., sodium hydrogen carbonate and sodium carbonate are preferred.
• Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds, and calcium acetate monohydrate and magnesium acetate tetrahydrate are preferred.
• Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, and amines.
• salts of zinc, tin, zirconium, and lead are preferably used, and these can be used alone or in combination. They may also be used in combination with the above-mentioned alkali metal compounds and alkaline earth metal compounds.
• transesterification catalyst examples include aluminum tris(2,4-pentanedionato)(III), diethyl (4-methylbenzyl)phosphonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride(II), tin chloride(IV), tin acetate(II), tin acetate(IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate(II), lead acetate(IV), zirconium acetate, and titanium tetrabutoxide.
• zinc acetate, zirconium acetate, aluminum tris(2,4-pentanedionato)(III), and diethyl (4-methylbenzyl)phosphonate are preferred, and aluminum tris(2,4-pentanedionato)(III) and diethyl (4-methylbenzyl)phosphonate are more preferred.
• aluminum or a compound thereof may also be used as a polymerization catalyst.
• the aluminum or its compound used as the polymerization catalyst can have a certain degree of catalytic activity by itself as a catalyst for polymerizing polyester carbonate by transesterification.
• Examples of such aluminum or its compound include metallic aluminum, aluminum salts, aluminum chelate compounds, organic aluminum compounds, inorganic aluminum compounds, etc.
• Aluminum salts include organic and inorganic salts of aluminum.
• organic salts of aluminum include aluminum carboxylates, specifically aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate.
• inorganic salts of aluminum include aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, and aluminum phosphonate.
• Aluminum chelate compounds include, for example, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum ethylacetoacetate diisopropoxide.
• Organoaluminum compounds include aluminum alkoxides such as trialkylaluminum, dialkylaluminum alkoxides, alkylaluminum dialkoxides, aluminum trialkoxides, and hydrolysates thereof. Specific examples include aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide, trimethylaluminum, triethylaluminum, and hydrolysates thereof. Inorganic aluminum compounds include aluminum oxide.
• Aluminum carboxylates, inorganic acid salts and chelate compounds are particularly preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.
• phosphorus compounds may also be used as polymerization catalysts.
• the phosphorus compound used as a polymerization catalyst can improve the catalytic activity of aluminum or its compound in the polymerization reaction of polyester carbonate. Without being bound by theory, it is believed that this is because the phosphorus compound can prevent the catalytic activity of aluminum or its compound from being deactivated by alcohol or water present in the reaction system.
• Such phosphorus compounds include, for example, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphineous acid compounds, and phosphine compounds.
• phosphonic acid compounds, phosphinic acid compounds, and phosphine oxide compounds can be mentioned, and in particular, phosphonic acid compounds can be mentioned.
• the phosphonic acid compound refers to a compound having the following structure:
• Examples of phosphonic acid compounds include dimethyl methylphosphonate, diethyl methylphosphonate, dihexyl methylphosphonate, dioctyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dihexyl phenylphosphonate, dioctyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, dihexyl benzylphosphonate, dioctyl benzylphosphonate, diphenyl benzylphosphonate, dimethyl p-methylbenzylphosphonate, and p-methylbenzyl
• Examples of the hydroxybenzylphosphonic acid include diethyl p-methylbenzylphosphonic acid, dihexyl p-methylbenzylphosphonic acid, dioctyl
• the phosphinic acid compound refers to a compound having the following structure:
• phosphinic acid compounds include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, and phenyl phenylphosphinate.
• the phosphine oxide compound refers to a compound having the following structure:
• phosphine oxide compounds include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.
• the phosphonous acid compound refers to a compound having the following structure:
• Examples of phosphonite compounds include dimethyl phosphonite, diethyl phosphonite, dipropyl phosphonite, dibutyl phosphonite, and diphenyl phosphonite.
• the phosphinous acid compound refers to a compound having the following structure:
• Examples of phosphonous acid compounds include hydroxyphosphine, methyl dibutylphosphinite, propyl diphenylphosphine, methoxydiphenylphosphine, and ethoxydiphenylphosphine.
• the phosphine compound refers to a compound having the following structure:
• phosphine compounds include trimethylphosphine, triethylphosphine, methyldibutylphosphine, and phenylisopropylphosphine.
• phosphorus compounds having aromatic rings are particularly preferred, and phosphonic acid compounds having aromatic ring structures are particularly preferred.
• the phosphorus compound may be a compound represented by the following general formulas (P7) to (P9).
• P( O)R 4.000 (OR p )(OR q ) ...(P7)
• P( O)R 4.000 R r (OR p )...(P8)
• R s R t each independently represent a hydrogen atom or a hydrocarbon group having 1 to 50 or 1 to 20 carbon atoms which may contain a hydroxyl group, a halogen group, an alkoxyl group or an amino group and which may have an alicyclic structure or an aromatic ring structure
• R p and R q each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 or 1 to 5 carbon atoms).
• R o , R r , R s and/or R t have an aromatic ring, particularly a benzyl group, and it is also preferred that R p and R q are hydrogen or a hydrocarbon group having 1 to 3 carbon atoms.
• catalysts are used so that the metal components in the catalyst are preferably 0.1 to 10 ppm, more preferably 0.1 to 7.0 ppm, even more preferably 0.1 to 5.0 ppm, even more preferably 0.1 to 3.0 ppm, and particularly preferably 0.1 to 1.0 ppm, relative to the amount of resin theoretically produced.
• the melt polycondensation method uses the above-mentioned raw materials and catalyst and carries out melt polycondensation under heating at normal or reduced pressure while removing by-products through an ester exchange reaction. Specifically, the reaction is carried out at a temperature of 120 to 260°C, preferably 180 to 260°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum in the reaction system to react the diol compound with the carbonate diester, and finally, the polycondensation reaction is carried out at a temperature of 200 to 350°C for 0.05 to 2 hours under a reduced pressure of 1 mmHg or less. Such a reaction may be carried out continuously or batchwise.
• the reaction apparatus used in carrying out the above reaction may be a vertical type equipped with an anchor-type stirring blade, a Max Blend stirring blade, a helical ribbon-type stirring blade, or the like, a horizontal type equipped with a paddle blade, a lattice blade, a spectacle blade, or the like, or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
• the catalyst may be removed or deactivated after the polymerization reaction is completed in order to maintain thermal stability and hydrolytic stability.
• a method of deactivating the catalyst by adding a known acidic substance is preferably carried out.
• esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphoric acid esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate,
• Suitable examples of the deactivating agent include phosphate esters such as monooctyl phosphate and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane, boronic acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzoyl chloride.
• phosphate esters such as monooct
• aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate.
• these deactivators are used in an amount of 0.01 to 50 times by mole, preferably 0.3 to 20 times by mole, relative to the amount of the catalyst. If the amount is less than 0.01 times by mole, the deactivating effect is insufficient, which is not preferable. Furthermore, if the amount is more than 50 times the amount of catalyst, the heat resistance decreases and the molded product becomes more likely to become discolored, which is not preferable.
• a step may be added in which the low-boiling compounds in the polymer are removed by volatilization at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C.
• a horizontal device equipped with stirring blades with excellent surface renewal capabilities such as paddle blades, lattice blades, and spectacle blades, or a thin-film evaporator is preferably used.
• the polyester carbonate resin of the preferred embodiment of the present invention is desired to have as little foreign matter content as possible, and filtration of the molten raw material and the catalyst liquid is preferably carried out.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
• filtration of the produced resin with 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 process of collecting the resin pellets must naturally be in a low-dust environment, and is preferably class 1000 or less, more preferably class 100 or less.
• the polyester resin of the preferred embodiment of the present invention can be produced by a conventionally known polyester production method using the crystals of the dicarboxylic acid diester constituting the above-mentioned structural unit (A) and a diol compound.
• the melt polymerization method such as the transesterification method and the direct esterification method, or the solution polymerization method can be mentioned.
• the above-mentioned diol compound can be an aliphatic dihydroxy compound or an aromatic dihydroxy compound as mentioned above, and the monomer represented by the above-mentioned general formula (b) and/or the monomer represented by the above-mentioned general formula (c) can be mentioned preferably.
• an ester exchange catalyst, an esterification catalyst, a polycondensation catalyst, etc. which are used in the production of ordinary polyester resins, can be used.
• These catalysts are not particularly limited, but examples include compounds of metals such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, germanium, and tin (e.g., fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, and alkoxides), and metallic magnesium. These can be used alone or in combination of two or more.
• the catalyst among the above, compounds of manganese, cobalt, zinc, titanium, calcium, antimony, germanium, and tin are preferred, and compounds of manganese, titanium, antimony, germanium, and tin are more preferred.
• the amount of these catalysts used is not particularly limited, but the amount of metal components relative to the raw material of the polyester resin is preferably 1 to 1000 ppm, more preferably 3 to 750 ppm, and even more preferably 5 to 500 ppm.
• the reaction temperature in the polymerization reaction depends on the type of catalyst and its amount used, but is usually selected in the range of 150°C to 300°C, with 180°C to 280°C being preferred when considering the reaction rate and coloring of the resin.
• the pressure in the reaction chamber is preferably adjusted from atmospheric pressure to 1 kPa or less, and more preferably to 0.5 kPa or less.
• a phosphorus compound When carrying out the polymerization reaction, a phosphorus compound may be added as desired.
• phosphorus compounds include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid esters, and phosphorous acid esters.
• phosphorous acid esters include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphenyl phosphate.
• phosphorous acid esters include, but are not limited to, methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite. These may be used alone or in combination of two or more.
• the concentration of phosphorus atoms in the polyester resin of the present invention is preferably 1 to 500 ppm, more preferably 5 to 400 ppm, and even more preferably 10 to 200 ppm.
• polyester resin of the preferred embodiment of the present invention various stabilizers such as etherification inhibitors, heat stabilizers, and light stabilizers, polymerization regulators, etc. can be used.
• thermoplastic resin ⁇ Physical properties of thermoplastic resin> (1) Weight average molecular weight (Mw) calculated as polystyrene
• 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. Mw can be measured by the method described in the Examples below.
• the YI value of the thermoplastic resin is preferably 0.1 to 14, more preferably 0.1 to 10, further preferably 0.1 to 7, and particularly preferably 0.3 to 5.
• the YI value can be measured by the method described in the examples below.
• one of the features of the thermoplastic resin is that it has a high refractive index, and the refractive index is preferably 1.600 to 1.700, more preferably 1.626 to 1.700, and particularly preferably 1.630 to 1.650.
• the Abbe number of the thermoplastic resin is preferably from 22.0 to 26.0, more preferably from 23.0 to 26.0, and particularly preferably from 23.0 to 24.7.
• one of the characteristics of the thermoplastic resin is high heat resistance, and the glass transition temperature (Tg) is preferably 70 to 200°C, more preferably 100 to 200°C, even more preferably 100 to 150°C, even more preferably 125 to 150°C, even more preferably 125 to 145°C, and particularly preferably 125 to 140°C.
• one of the characteristics of the thermoplastic resin is that it has a low photoelastic coefficient.
• the photoelastic coefficient is preferably 25 to 45, more preferably 25 to 38, and particularly preferably 30 to 38.
• 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, and making it possible to reduce weight and molding costs.
• Aspherical lenses are therefore 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 having one convex side and one 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 (Mw) The weight average molecular weight (Mw) of the obtained resin was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene.
• GPC gel permeation chromatography
• GPC device Tosoh Corporation, HLC-8420GPC Column: 3 TSKgel SuperHM-M, manufactured by Tosoh Corporation 1 TSKgel guardcolumn SuperH-H, manufactured by Tosoh Corporation 1 TSKgel SuperH-RC, manufactured by Tosoh Corporation 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 Column temperature: 40°C
• the internal temperature was cooled to 85°C to precipitate crystals without adding seed crystals, and then the internal temperature was cooled to 5°C at a cooling rate of 10°C/hour. Subsequently, the crystals precipitated at the same temperature were filtered off, and the obtained crystals were dried under reduced pressure at 1.3 kPa for 11 hours while being heated in a water bath at 90° C., thereby obtaining 73.2 g of a compound represented by the following formula (1) as crystals (yield: 76%).
• the maximum melting endothermic temperature of the obtained crystals of the compound represented by formula (1) was measured by differential scanning calorimetry (DSC) according to the method described below, and was found to be 179.1°C.
• the thermal decomposition temperature (Td5) of the obtained crystals of the compound represented by formula (1) was measured by differential thermobalance according to the method described below, and was found to be 330.4°C.
• the main X-ray diffraction peaks (having a relative intensity of more than 5%) obtained by powder X-ray diffraction according to the method described below for the obtained crystals of the compound represented by formula (1) are shown in Table 1 below.
• DSC Differential Scanning Calorimetry
• Td5 ⁇ Measurement of thermal decomposition temperature (Td5)> Using a differential thermobalance (Rigaku Corporation, "Thermo plus EVO2"), 5 mg of crystals were precisely weighed out in an aluminum pan, and the other aluminum pan was set empty. After the weight value was set to zero, the temperature was raised to 450°C at a heating rate of 10°C/min in a nitrogen atmosphere, and the thermal decomposition temperature was measured. The thermal decomposition temperature was the temperature at which the weight was reduced by 5%.
• Measurement range: 2 ⁇ 5° to 70°
• Scan speed: 2 ⁇ 2°/min
• Slit: DS 1°
• mask 15 mm
• RS variable (from 0.1 mm).
• Example 1 As raw materials, 167.63 g (0.302 mol) of crystals of BINOL-DP synthesized in Synthesis Example 1, 128.73 g (0.239 mol) of BNEF represented by the following structural formula, 60.53 g (0.162 mol) of BNE, 21.50 g (0.100 mol) of DPC (diphenyl carbonate), and 0.7 mg (4.0 ⁇ 10 -6 mol) of calcium acetate monohydrate were placed in a 500 mL reactor equipped with a stirrer and a distillation device, and the raw materials were dissolved while stirring for 10 minutes at a heat medium temperature of 200 ° C. under a nitrogen atmosphere of 101.3 kpa. The heat medium temperature was then raised to 220 ° C.
• Example 2 A polyester carbonate resin was obtained in the same manner as in Example 1, except that the amount of the catalyst was changed to the amount shown in Table 2. The physical properties of the obtained resin are shown in Table 2.
• Example 5 Polyester carbonate resins were obtained in the same manner as in Example 1, except that the catalyst type was changed to the catalyst shown in Table 2. The physical properties of the obtained resins are shown in Table 2.
• Example 1 A polyester carbonate resin was obtained in the same manner as in Example 1, except that the crystals of BINOL-DP (phenyl ester) were replaced with BINOL-DC (carboxylic acid) represented by the following structural formula.
• BINOL-DP phenyl ester
• BINOL-DC carboxylic acid
• Example 2 A polyester carbonate resin was obtained in the same manner as in Example 1, except that the crystals of BINOL-DP (phenyl ester) were replaced with BINOL-DM (methyl ester) represented by the following structural formula.
• BINOL-DP phenyl ester
• BINOL-DM methyl ester
• Comparative Example 3 A polyester carbonate resin was obtained in the same manner as in Comparative Example 2, except that the amount of the catalyst was changed to the amount shown in Table 2. The physical properties of the obtained resin are shown in Table 2.

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• 2024
  • 2024-02-07 JP JP2025501089A patent/JPWO2024171914A1/ja active Pending
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