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
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
• • 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
  • C08G64/02—Aliphatic polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
• • 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
  • C08G64/22—General preparatory processes using carbonyl halides
  • C08G64/226—General preparatory processes using carbonyl halides and alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
  • C08L69/005—Polyester-carbonates
• • 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

Definitions

• the present invention relates to a novel thermoplastic resin composition and an optical lens or film formed by it.
• a preferred embodiment of the present invention relates to a thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue and haze.
• Optical glass or optical transparent resin is used as a material for optical elements used in the optical system of various cameras such as cameras, film-integrated cameras, and video cameras.
• Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are various types of materials with various refractive indices (nD) and Abbe numbers ( ⁇ D), but the material cost is high. In addition to being high, it has problems of poor moldability and low productivity. In particular, processing an aspherical lens used for aberration correction requires extremely high technology and high cost, which is a major obstacle to practical use.
• transparent lenses for optics especially optical lenses made of thermoplastic transparent resin
• Is used as. Examples thereof include polycarbonate made of bisphenol A, polystyrene, poly-4-methylpentene, polymethylmethacrylate, and amorphous polyolefin.
• the transparent resin for optics is used as an optical lens
• transparency, heat resistance, and low birefringence are required in addition to the refractive index and the Abbe number, so that the use location is limited by the characteristic balance of the resin.
• polystyrene has low heat resistance and high birefringence
• poly-4-methylpentene has low heat resistance
• polymethylmethacrylate has low glass transition temperature, low heat resistance, and low refractive index, so its application area is limited.
• Polycarbonate composed of bisphenol A is not preferable because it has weak points such as large birefringence and is limited in places of use.
• a lens element having the same refractive index can be realized by a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, and Since it is possible to reduce the size and weight of the lens system by reducing the decentering sensitivity and the lens thickness, it is useful to increase the refractive index.
• CMOS complementary metal-oxide-semiconductor
• CMOS complementary metal-oxide-semiconductor
• cycloolefin polymers have been widely used for optical lens applications because of their excellent heat resistance and excellent mechanical properties.
• Polyester and polycarbonate are examples of low Abbe number resins.
• the resin described in Patent Document 1 is characterized by a high refractive index and a low Abbe number.
• Patent Documents 2 to 4 describe polycarbonate copolymers containing a perhydroxydimethanonaphthalene skeleton. However, since the positions of dihydroxymethyl groups are all at the 2 and 3 positions, the strength is weak and it is suitable for optical lens applications. Is not suitable. Furthermore, the polycarbonates described in Patent Documents 2 to 4 have a low glass transition temperature (Tg), and therefore have a problem in heat resistance. For example, the polycarbonate of HOMO described in Example 1 of Patent Document 4 has a low glass transition temperature (Tg) of 125 ° C. despite having a number average molecular weight of 38,000.
• Tg glass transition temperature
• the present invention aims to solve at least one of the above-mentioned conventional problems. Further, a preferred embodiment of the present invention aims to provide a thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze. .
• thermoplastic resin composition can solve the above problems, and have reached the present invention.
• thermoplastic resin composition containing a thermoplastic resin containing a structural unit represented by the following formula (1):
• a terminal structure of the thermoplastic resin includes a structure represented by the following formula (A) or formula (B), and the thermoplastic resin has a polystyrene-reduced weight average molecular weight of 1,000 to 50,000. It is a plastic resin composition.
• thermoplastic resin composition according to ⁇ 1> wherein the thermoplastic resin further contains a structural unit represented by the following formula (2).
• R represents hydrogen, a methyl group, or an ethyl group.
• thermoplastic resin further contains a structural unit represented by the following formula (3).
• R represents hydrogen, a methyl group, or an ethyl group.
• the mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (A) is represented by the structural unit represented by the formula (1): the formula (A).
• the constitutional unit 97.0: 3.00 to 99.99: 0.01, which is the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 3> above.
• the mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (B) is represented by the structural unit represented by the formula (1): the formula (B).
• the constitutional unit is 99.00: 1.00 to 99.99: 0.01, and the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 3> above.
• thermoplastic resin composition according to ⁇ 2> The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is represented by the structural unit represented by the formula (1): the formula (2).
• the structural unit is 98.0: 2.00 to 99.99: 0.01.
• the mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (3) is represented by the structural unit represented by the formula (1): the formula (3).
• the constitutional unit is 98.0: 2.00 to 99.99: 0.01, and the thermoplastic resin composition according to ⁇ 3> above.
• carboxylic acid salt in Ra is sodium carboxylate.
• R 1 and R 2 are each independently 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 carbon atom. Selected from the group consisting of a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom; and X's each independently being branched.
• thermoplastic resin composition (A good alkylene group having 1 to 6 carbon atoms; n is each independently an integer of 0 to 5.)
• n is each independently an integer of 0 to 5.
• the additive contains two or more kinds of antioxidants and a release agent.
• the content of the antioxidant is 0.50% by mass or less in the thermoplastic resin composition
• the content of the release agent is 0.50% by mass or less in the thermoplastic resin composition.
• thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 14>, which contains at least one monomer selected from the group consisting of the compounds represented by (d).
• thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 15>, which has a specific heat capacity of 450 J / g ⁇ ° C or less.
• thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 16>, wherein the thermoplastic resin is polycarbonate, polyester carbonate, or polyester.
• thermoplastic resin composition An optical lens using the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 17>.
• ⁇ 19> A film using the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 17>.
• ⁇ 20> At least a dihydroxy compound represented by the following formula (I), Selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d)
• a method of producing a thermoplastic resin composition by reacting at least one compound with The production method is such that the total amount of the at least one compound is 10% or less with respect to the mass of the dihydroxy compound represented by the formula (I).
• R represents hydrogen, a methyl group, or an ethyl group.
• Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.
• Rb represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.
• thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze. Also, an optical lens or film produced from this resin composition can be obtained.
• thermoplastic resin of the present invention contains a structural unit represented by the following formula (1) (hereinafter referred to as “structural unit (1)”). Examples thereof include structural units derived from decahydro-1,4: 5,8-dimethanonaphthalenediol (sometimes referred to as D-NDM). As will be described later, the structural unit (1) is obtained, for example, by reacting a diol compound represented by the formula (I) with a carbonic acid diester.
• the thermoplastic resin of the present invention include polycarbonate, polyester carbonate, and polyester. Among them, polycarbonate resin is preferred.
• R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.
• the terminal structure of the thermoplastic resin of the present invention includes a structure represented by the following formula (A) or formula (B).
• Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.
• the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester.
• carboxylate sodium carboxylate is preferably mentioned.
• the mass of the structural unit represented by the formula (A) is less than the above range, at least one of specific heat capacity, hue, and haze may be inferior.
• the mass of the structural unit represented by the formula (A) is more than the above range, the hue and heat resistance of the polymer may be deteriorated.
• the mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (B) is represented by the constitutional unit represented by the formula (1): the formula (B).
• Structural unit 99.00: 1.00 to 99.99: 0.01 is preferable, 99.00: 1.00 to 99.95: 0.05 is more preferable, and 99.50: 0.50 to 99. 90: 0.10 is more preferable, and 99.70: 0.30 to 99.90: 0.10 is particularly preferable.
• the mass of the structural unit represented by the formula (B) is less than the above range, at least one of specific heat capacity, hue, and haze may be inferior.
• thermoplastic resin of the present invention preferably has both the structure represented by the formula (A) and the structure represented by the formula (B) from the viewpoint of specific heat capacity.
• the thermoplastic resin of the present invention may contain other structural units in addition to the resin having only the structural unit (1) and the structure represented by the formula (A) or the formula (B).
• Preferred examples of the other structural unit include a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a structural unit represented by the following formula (4).
• R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.
• R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.
• R 1 and R 2 are each independently 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 carbon number. It is selected from the group consisting of a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom, and preferably selected from a hydrogen atom and a phenyl group.
• X's each independently represent an optionally branched alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably ethylene.
• n independently represents an integer of 0 to 5, preferably 1 or 2, and more preferably 1.
• Constitutional unit represented by the formula (2) 99.00: 2.00 to 100: 0 is preferable, 99.00: 2.00 to 99.99: 0.01 is more preferable, and 99.00: 1.00 to 99.99: 0.01 is preferable. More preferably, 99.05: 0.95 to 99.99: 0.01 is particularly preferable.
• Constitutional unit represented by the formula (3) 99.00: 2.00 to 100: 0 is preferable, 99.00: 2.0 to 99.99: 0.01 is more preferable, and 99.00: 1.00 to 99.99: 0.01 is preferable. More preferably, 99.05: 0.95 to 99.99: 0.01 is particularly preferable.
• Constitutional unit represented by the formula (4) 99: 1 to 1:99 is preferable, 90:10 to 10:90 is more preferable, 75:25 to 50:50 is further preferable, and 70:30 to 60:40 is particularly preferable.
• the mass of the structural unit represented by the above formula (4) is in the above range, the moldability is improved, and for example, the strength of the molded body such as impact strength is improved, which is preferable.
• thermoplastic resin of the present invention may contain other structural units in addition to the above structural units.
• Other constituent units that may be included include constituent units obtained by reacting a diol compound other than the formula (I) with a carbonic acid diester.
• Examples of the diol compound other than the formula (I) include bisphenol A and bisphenol AP.
• thermoplastic resin composition of the present invention is represented by the compound represented by the following formula (I), the compound represented by the following formula (a), the compound represented by the following formula (b), and the following formula (c). And a compound represented by the following formula (d), at least one of which is selected from the group consisting of compounds represented by the following formula (d), thereby reducing specific heat capacity, decreasing crystallinity, and reducing haze: It is preferable because the fluidity when melted for the molecular weight is improved and precision molding of an optical molded article or the like is facilitated.
• R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.
• Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.
• the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester.
• sodium carboxylate is preferably mentioned.
• Rb represents hydrogen, carboxylic acid, carboxylic acid ester, or carboxylic acid salt.
• the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester.
• sodium carboxylate is preferably mentioned.
• the polystyrene equivalent weight average molecular weight (Mw) of the thermoplastic resin of the present invention is 1,000 to 50,000.
• the weight average molecular weight (Mw) in terms of polystyrene is preferably 10,000 to 40,000, and more preferably 20,000 to 30,000. If the Mw is less than 1,000, the optical lens becomes brittle, which is not preferable. When the Mw is more than 50,000, the melt viscosity becomes high, so that it is difficult to remove the resin after production, and further, the fluidity is deteriorated and injection molding in a molten state becomes difficult, which is not preferable.
• the thermoplastic resin composition of the present invention may contain additives.
• the additive preferably contains two or more kinds of antioxidants and a release agent. The reason is that the antioxidant effect and the releasability are synergistically improved when two or more kinds of antioxidants and a release agent are added, rather than when they are added one by one.
• Antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 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-ter -Butyl-4-hydroxy-benzylphosphonate-diethyl este
• the release agent it is preferable that 90% by weight or more thereof is composed of an ester of alcohol and fatty acid.
• the ester of alcohol and fatty acid include an ester of monohydric alcohol and fatty acid, and a partial ester or total ester of polyhydric alcohol and fatty acid.
• the ester of monohydric alcohol and fatty acid is preferably ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms.
• the partial ester or total ester of polyhydric alcohol and fatty acid partial ester or total ester of polyhydric alcohol having 1 to 25 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms is preferable.
• ester of monohydric alcohol and saturated fatty acid examples include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate and isopropyl palmitate.
• the content of the release agent in the thermoplastic resin composition is preferably 0.50% by mass or less, more preferably 0.01 to 0.10% by mass, and 0.03 to 0. It is particularly preferable that the content is 05% by mass.
• thermoplastic resin composition of the present invention as other additives, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, a bluing agent or an antibacterial agent is added. You may.
• the diol compound represented by the above formula (I) includes dicyclopentadiene or cyclopentadiene and an olefin having a functional group, as shown in WO2017 / 175693. It can be synthesized as a raw material.
• thermoplastic resin of the present invention contains at least a dihydroxy compound represented by the following formula (I): Selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d)
• a method of producing a thermoplastic resin composition by reacting at least one compound with It can be produced by a production method in which the total amount of the at least one compound is 10% or less based on the mass of the dihydroxy compound represented by the formula (I).
• the total amount of the at least one compound is preferably 0.005 to 3.0%, and preferably 0.1 to 1.0, with respect to the mass of the dihydroxy compound represented by the formula (I).
• the total amount of the at least one compound is more than 10% with respect to the mass of the dihydroxy compound represented by the formula (I), the reactivity during polymerization is lowered, the molecular weight does not increase, and the pellets are stable. Cannot be transformed. Even if it can be pelletized, it cannot be stably molded, and a desired molded product cannot be obtained in a mold.
• the formula (a), the formula (b), and the formula (c) when Ra is hydrogen, the reactivity during the polymerization is lowered, and the molecular weight is difficult to increase.
• Ra in the formula (c) is a carboxylic acid or a carboxylic acid ester
• the hue of the resulting resin tends to deteriorate, and the heat resistance tends to deteriorate.
• R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.
• Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.
• carboxylic acid ester examples include carboxylic acid methyl ester and carboxylic acid phenyl ester. Further, as the carboxylate, sodium carboxylate is preferably mentioned.
• Rb represents hydrogen, carboxylic acid, carboxylic acid ester, or carboxylic acid salt.
• carboxylic acid ester examples include carboxylic acid methyl ester and carboxylic acid phenyl ester. Further, as the carboxylate, sodium carboxylate is preferably mentioned.
• thermoplastic resin of the present invention is a polycarbonate resin
• a diol compound represented by the formula (I) at least one of the compounds represented by the formulas (a) to (d), and a carbonic acid diester are used as raw materials. It can be produced by a melt polycondensation method.
• 2,6-position isomer: 2,7-position isomer 20: 80 to 80:20
• more preferably 2,6-position isomer: 2,7-position isomer 50: 50 to 80:20.
• other diol compounds may be used together.
• the polycondensation catalyst can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst composed of both.
• carbonic acid diesters examples 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 preferable from the viewpoint of reactivity and purity.
• the carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, based on 1 mol of the diol component.
• the molecular weight of the polycarbonate resin is controlled by adjusting this molar ratio.
• Examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• alkali metal compound used in the present invention examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals.
• Sodium carbonate and sodium hydrogen carbonate are preferable from the viewpoints of catalytic effect, price, distribution amount, influence on the hue of resin, and the like.
• alkaline earth metal compound examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkaline earth metal compounds.
• nitrogen-containing compounds include quaternary ammonium hydroxide and salts thereof, amines and the like.
• salts of zinc, tin, zirconium and lead are preferably used, and these can be used alone or in combination. Further, it may be used in combination with the above-mentioned alkali metal compound or alkaline earth metal compound.
• These catalysts are used in a ratio of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 3 mol, preferably 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mol, based on 1 mol of the total amount of the diol compound. .
• the melt polycondensation method is a method of performing melt polycondensation using the above-mentioned raw materials and catalysts while removing by-products by transesterification under heating under normal pressure or reduced pressure.
• the reaction is generally carried out in multiple stages of two or more stages.
• the first stage reaction is carried out at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Then, the reaction temperature is raised while raising the degree of vacuum in the reaction system to react the diol compound with the carbonic acid diester, and finally polycondensation is carried out under a reduced pressure of 1 mmHg or less at a temperature of 200 to 350 ° C for 0.05 to 2 hours. Perform the reaction. Such a reaction may be carried out continuously or batchwise.
• the reactor used when carrying out the above reaction is a vertical type equipped with an anchor type stirring blade, Maxblend stirring blade, helical ribbon type stirring blade, etc., but equipped with paddle blades, lattice blades, eyeglass blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reactor in which these are appropriately combined in consideration of the viscosity of the polymer.
• the catalyst may be removed or deactivated after the completion of the polymerization reaction in order to maintain thermal stability and hydrolysis stability.
• a method of deactivating the catalyst by adding a known acidic substance is preferably carried out.
• butyl p-toluenesulfonate is used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times the molar amount of the catalyst.
• the amount is less than 0.01 times the molar amount of the catalyst, the deactivating effect becomes insufficient, which is not preferable.
• the amount is more than 50 times the molar amount of the catalyst, the heat resistance is lowered and the molded product is easily colored, which is not preferable.
• a step of devolatilizing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided.
• paddle blades, lattice blades, glasses A horizontal device provided with a stirring blade having excellent surface renewal ability, such as a blade, or a thin film evaporator is preferably used.
• the thermoplastic resin of the present invention is desired to have a foreign matter content as small as possible, and thus the molten raw material and the catalyst liquid are preferably filtered.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less. Further, 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 step of collecting the resin pellets must be in a low dust environment, and is preferably class 1000 or less, more preferably class 100 or less.
• thermoplastic resin of a preferred embodiment of the present invention is excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze.
• the specific heat capacity of the thermoplastic resin of the present invention is preferably 450 J / g ⁇ ° C. or less, more preferably 1 to 400 J / g ⁇ ° C. G, further preferably 50 to 300 J / g ⁇ ° C., further preferably 100 to 300 J / g ⁇ ° C. Is more preferable, and 200 to 300 J / g ⁇ ° C. is particularly preferable.
• the specific heat capacity is 450 J / g ⁇ ° C.
• the glass transition temperature (Tg) of the thermoplastic resin of the present invention is preferably 95 to 180 ° C, more preferably 110 to 160 ° C, and particularly preferably 120 to 160 ° C. If the Tg is lower than 95 ° C., the operating temperature range of the lens or camera becomes narrow, which is not preferable. Further, if the temperature exceeds 180 ° C., the molding conditions for injection molding become strict, which is not preferable.
• the thermoplastic resin of the present invention preferably has a refractive index of 1.50 to 1.65 measured by the method of JIS-K-7142 after molding, and more preferably 1.53 to 1.58.
• the thermoplastic resin of the present invention has an Abbe's number of 25 or more, preferably 35 or more, more preferably 45 or more, measured by the method of JIS-K-7142 after molding. The upper limit of the Abbe number is about 55.
• the hue (YI) of the thermoplastic resin of the present invention is preferably 0.1 to 5.0, more preferably 1.0 to 3.5, and particularly preferably 2.0 to 3.0.
• the haze (Hz) of the thermoplastic resin of the present invention is preferably 0.1 to 0.5, more preferably 0.1 to 0.2.
• thermoplastic resin of the present invention phenol produced during production and carbonic acid diester remaining without reaction may be present as impurities.
• the phenol content in the thermoplastic resin is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, and 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. Is particularly preferred.
• the content of carbonic acid diester in the thermoplastic resin is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm.
• the strength of the obtained resin molded product may be reduced, and problems such as odor may occur.
• the content of phenol or carbonic acid diester is less than the above range, the plasticity at the time of melting the resin may decrease.
• the optical lens of the present invention can be obtained by injection molding the above-mentioned thermoplastic resin of the present invention into a lens shape by an injection molding machine or an injection compression molding machine.
• the molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 300 ° C, more preferably 180 to 290 ° C.
• the injection pressure is preferably 50 to 1700 kg / cm 2 .
• the molding environment In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment must also be a low dust environment, and is preferably class 1000 or lower, more preferably class 100 or lower.
• the optical lens of the present invention is preferably used in the form of an aspherical lens, if necessary. Since an aspherical lens can reduce the spherical aberration to substantially zero with one lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the production cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
• the astigmatism of the aspherical lens is preferably 0 to 15 m ⁇ , more preferably 0 to 10 m ⁇ .
• the thickness of the optical lens of the present invention can be set in a wide range according to the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm.
• a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens of the present invention.
• the antireflection layer may be a single layer or a multilayer, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride.
• the antireflection layer is not particularly limited in the combination of single layer / multilayer and the combination of components and thickness thereof, but preferably has a two-layer structure or a three-layer structure, particularly preferably a three-layer structure.
• the antireflection layer as a whole is preferably formed with a thickness of 0.0017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 ⁇ m, particularly preferably 1 to 2 ⁇ m.
• the content of the monomer was measured by gas chromatography (manufacturing equipment: Shimadzu Corporation GC-2010 Plus) using a mixture of 1 mass% methanol solution under a temperature-raising vaporization method of 50 to 300 ° C. It is the value that was performed. The same applies hereinafter.
• Compound d 1.0000 mass%
• Mixture I-1 A mixture I-1 was obtained by the same method as "monomer synthesis example 1" shown in WO2017 / 175693 (distillation purification x 1 time). In addition to the main product, Compound Ip, this mixture I-1 also contained the compounds a, b, c-1, c-2, and d as impurities as impurities in the following contents. Was there. Compound a: 1.4000 mass% Compound b: 0.5000 mass% Compound c-1: 1.8000 mass% Compound c-2: 0.0100% by mass Compound d: 0.0100 mass%
• Mixture I-2 The mixture I-1 obtained above was distilled again (distillation purification: twice in total) to obtain a mixture I-2.
• This mixture I-2 contained, as impurities, the compounds a, b, c-1 and c-2, which were monomers, in addition to the main product, the compound Ip, in the following contents.
• Compound c-1 0.6100% by mass
• Compound c-2 0.0100% by mass
• Compound d below detection limit (less than 0.0001 mass%)
• the mixture I-2 obtained above was distilled again (distillation purification: 3 times in total) to obtain a mixture I-3.
• This mixture I-3 contained, as impurities, the compounds a, b and c-1 which were the monomers, in addition to the main product, the compound Ip, in the following contents.
• Compound a 0.3400 mass%
• Compound b 0.1100% by mass
• Compound c-1 0.0200 mass%
• Compound c-2 below detection limit (less than 0.0001 mass%)
• Compound d below detection limit (less than 0.0001 mass%)
• Mw ⁇ (Wi ⁇ Mi) ⁇ ⁇ (Wi)
• i the i-th division point when the molecular weight M is divided
• Wi the i-th weight
• Mi the i-th molecular weight.
• the molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve.
• HLC-8320GPC manufactured by Tosoh Corporation was used as a GPC device, one TSKguardcolumn SuperMPHZ-M was used as a guard column, and three TSKgel SuperMultiporeHZ-M were connected in series as an analytical column. Other conditions are as follows.
• thermoplastic resin composition was press-molded (molding conditions: 200 ° C., 100 kgf / cm 2 , 2 minutes) on a disc having a diameter of 40 mm and a thickness of 3 mm, cut out at a right angle, and measured by KPR-200 manufactured by Karnew.
• ⁇ Glass transition temperature (Tg)> Based on JIS K7121-1987, it was measured by a differential scanning calorimeter (DSC). As the analyzer, Hitachi High-Tech Science X-DSC7000 was used. ⁇ Method of measuring hue (YI) and haze (Hz)> Using an injection molding machine SH50 manufactured by Sumitomo Heavy Industries, Ltd., injection molding was carried out at a cylinder temperature of 260 ° C. and a mold temperature of 30 ° C. lower than the glass transition temperature of the resin to obtain a 3 mm thick disc. Hue (YI) and haze (Hz) were measured using this disc. The hue (YI) was measured by SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the haze (Hz) was measured by NDH2000 manufactured by Nippon Denshoku.
• BPEF represented by the following structural formula: 1.000 mol (438.52 g), sodium hydrogencarbonate: 1 ⁇ 10 ⁇ 6 mol (0.084 mg, added as a 1% by mass aqueous solution) and diphenyl carbonate.
• Polycarbonate resin W was obtained by reacting and pelletizing in the same manner as the above-mentioned polycarbonate resin A except that 1.020 mol (218.50 g) was used. Subsequently, the pellets were dried at 110 ° C. for 3 hours.
• Stearate (Riken Vitamin Co., Ltd .; Rikemal S-100A) 0.20% by mass, antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ( ADEKA CORPORATION; ADEKA STAB AO-60) 0.10% by weight, antioxidant 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10 -Tetraoxa-3,9-diphosphaspiro [5.5] undecane (A Co., Ltd.
• Examples 2 to 11, Comparative Examples 1 and 2 Polycarbonate resins B to K were obtained in the same manner as in Example 1 except that the raw materials and the charged amounts shown in Table 2 were changed.
• a polycarbonate resin composition was obtained in the same manner as in Example 1 except that the polycarbonate resins B to K were used instead of the polycarbonate resin A and the additives and the amounts of the additives shown in Table 1 were used instead.
• the physical properties of the obtained polycarbonate resin composition are shown in Table 1.
• S-100A Glycerin monostearate (Riken Vitamin Co., Ltd .; Rikemar S-100A) which is a release agent B-100A: Glycerin monobehenate as a release agent (manufactured by Riken Vitamin Co., Ltd .; Rikemar B-100A)
• Poem M-100 Glycerin monocaprylate (Riken Vitamin Co., Ltd .; Poem M-100) as a release agent
• Poem M-300 Glycerin monolaurate as a release agent (Riken Vitamin Co., Ltd .; Poem M-300)
• AO-60 Antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation; ADEKA STAB AO-60) AO-30: [4,4 ′, 4
• Example A The same procedure as in Example 1 was repeated except that, instead of the compound Ip, the mixture I-1 obtained above was 222.33 g, sodium hydrogencarbonate was 8.4 mg, and diphenyl carbonate was 221.90 g. A polycarbonate resin composition was obtained. Table 3 shows the physical properties of the obtained polycarbonate resin composition.
• Example A-1 to Example C-2) The same procedure as in Example A was carried out except that the raw materials and the charged amounts shown in Table 3 were changed. Table 3 shows the physical properties of the obtained polycarbonate resin composition.
• an optical lens excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze can be obtained.
• the optical lens of the present invention can be injection-molded, has high productivity, and is inexpensive. Therefore, it can be used in fields where expensive high-Abbe glass lenses have been conventionally used, such as cameras, telescopes, binoculars, and television projectors. It is useful. Further, since the difference in water absorption between the high Abbe lens and the low Abbe lens becomes small, it is particularly suitable for a small optical lens unit. Further, according to the present invention, a high Abbe aspherical lens, which is technically difficult to process with a glass lens, can be easily obtained by injection molding, which is extremely useful.

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