Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
  • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a novel polycarbonate resin composition and an optical lens formed therefrom.
• Optical glass or optical transparent resin is used as a material for optical elements used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras.
• Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indices (nD) and Abbe numbers ( ⁇ D).
• nD refractive indices
• ⁇ D Abbe numbers
• the processing of an aspherical lens used for aberration correction requires extremely advanced technology and high cost, which poses a major obstacle for practical use.
• optical lenses made from optical transparent resins can be mass-produced by injection molding.
• polycarbonate consisting of bisphenol A, polystyrene, poly-4-methylpentene, polymethyl methacrylate, amorphous polyolefin and the like are exemplified.
• optical transparent resin when used as an optical lens, transparency, heat resistance, and low birefringence are required in addition to the refractive index and Abbe number. It has weaknesses. For example, polystyrene has low heat resistance and high birefringence, poly-4-methylpentene has low heat resistance, and polymethyl methacrylate has a low glass transition temperature, low heat resistance, and a small refractive index, so its application range is limited. , and bisphenol A have weak points such as large birefringence, and are limited in places where they can be used.
• a method of correcting chromatic aberration by combining a plurality of lenses with different Abbe numbers is known.
• a lens made of a cycloolefin resin having a relatively high Abbe number and a lens made of a polycarbonate resin made of bisphenol A having a relatively low Abbe number are combined to correct chromatic aberration.
• there is a difference in the water absorption expansion rate between cycloolefin resin and polycarbonate resin and when a lens unit is formed by combining both lenses, there is a difference in the size of the lens when it absorbs water in the usage environment such as a smartphone. do. This expansion coefficient difference impairs the performance of the lens.
• Patent Documents 1 to 3 describe polycarbonate copolymers containing a perhydroxydimethanonaphthalene skeleton. is not suitable.
• Patent Document 4 decahydro-1,4:5,8- Although a polycarbonate resin made from dimethanonaphthalenediol (D-NDM) is disclosed, further improvement in optical properties has been desired. Further, Patent Document 5 discloses a polycarbonate resin composition having a low birefringence, a medium refractive index, and a medium Abbe number without a decrease in hue (YI) or haze (Hz). Improvements in optical properties have been desired.
• D-NDM dimethanonaphthalenediol
• the problem to be solved by the present invention is to provide a polycarbonate resin composition having a low photoelastic coefficient, a medium refractive index, and a medium Abbe number, and an optical lens formed from this resin composition.
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and Y 1 and Y 2 each independently represent 1 to represents the alkylene group of 4.
• Y 1 and Y 2 each independently represent 1 to represents the alkylene group of 4.
• ⁇ 6> The polycarbonate resin composition according to any one of ⁇ 1> to ⁇ 5> above, wherein the polycarbonate resin composition has an Abbe number of 46 to 55.
• ⁇ 7> The polycarbonate resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polycarbonate resin composition has a refractive index (nD) of 1.533 to 1.547.
• nD refractive index
• ⁇ 8> The polycarbonate resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the polycarbonate resin composition has a Tg of 132 to 135°C.
• An optical lens comprising the polycarbonate resin composition according to any one of ⁇ 1> to ⁇ 8> above.
• the present invention it is possible to provide a polycarbonate resin composition having a low photoelastic coefficient, a medium refractive index, and a medium Abbe number, and an optical lens using the same.
• the polycarbonate resin composition of the present invention comprises a monomer-derived structural unit (A) represented by the following general formula (i), and a monomer-derived structural unit (B) represented by the following general formula (ii),
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, particularly preferably a hydrogen atom.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or a It represents a cycloalkyl group, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.
• R 1 and R 2 preferably represent a hydrogen atom, a methyl group or a phenyl group, more preferably a hydrogen atom or a phenyl group.
• R 3 and R 4 preferably represent a hydrogen atom.
• Y 1 and Y 2 each independently represent an alkylene group having 1 to 4 carbon atoms, preferably an ethylene group or a propylene group, more preferably an ethylene group.
• the polycarbonate resin (A) having the structural unit (A) and the structural unit (B ) may be a copolymer resin containing the structural unit (A) and the structural unit (B) in the same resin, but the former A more preferred embodiment is a resin mixture.
• the resin mixture which is a more preferred embodiment, will be described in detail below.
• Polycarbonate resin (A) in a preferred embodiment of the present invention has a structural unit (A) represented by the following general formula (1).
• R has the same definition as in general formula (i).
• the structural unit (A) represented by the general formula (1) is exemplified by a structural unit derived from the dihydroxy compound represented by the general formula (i).
• a structural unit derived from decahydro-1,4:5,8-dimethanonaphthalenediol hereinafter sometimes referred to as "D-NDM").
• the structural unit represented by the general formula (M) is exemplified by a structural unit derived from a dihydroxy compound represented by the following general formula (O), and the structural unit represented by the general formula (N) is Structural units derived from dihydroxy compounds represented by the following general formula (P) are exemplified.
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• P represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R is preferably the same, and from the viewpoint of flowability, R is preferably a hydrogen atom.
• the polycarbonate resin (A) in the present invention has the structural unit (A) represented by the above general formula (1), but may contain other structural units as long as the effects of the present invention are not impaired.
• the proportion of the structural unit (A) in the polycarbonate resin (A) in the present invention is preferably 70% by mass or more, more preferably 100% by mass.
• the other structural unit that may be contained in the polycarbonate resin (A) in the present invention is a structural unit obtained by reacting a diol compound other than the general formula (i) with a carbonic acid diester, and is a structural unit other than the general formula (i).
• diol compounds include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. etc. are exemplified.
• Polycarbonate resin (B) in a preferred embodiment of the present invention has a structural unit (B) represented by the following general formula (2).
• R 1 , R 2 , R 3 , R 4 , Y 1 and Y 2 have the same meanings as in general formula (ii).
• the structural unit (B) represented by the general formula (2) is exemplified by a structural unit derived from the dihydroxy compound represented by the general formula (ii).
• Specific examples of the fluorene diol compound represented by the general formula (ii) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl).
• Fluorene 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3- cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2 -hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy) -3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-
• BPEF 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene
• BPPEF 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene
• BPMEF 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene
• BPPEF 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene
• BPPEF 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene
• the polycarbonate resin (B) in the present invention has the structural unit (B) represented by the above general formula (2), but may contain other structural units as long as the effects of the present invention are not impaired.
• the proportion of the structural unit (B) represented by the general formula (2) in the polycarbonate resin (B) in the present invention is preferably 70% by mass or more, more preferably 100% by mass.
• the other structural unit that may be contained in the polycarbonate resin (B) in the present invention is a structural unit obtained by reacting a diol compound other than the general formula (ii) with a carbonic acid diester, and is a structural unit other than the general formula (ii).
• diol compounds include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. etc. are exemplified.
• a polycarbonate resin composition of a preferred embodiment of the present invention comprises a polycarbonate resin (A) having a structural unit (A) represented by the general formula (1), and a structural unit (B) represented by the general formula (2).
• Polycarbonate resin (B) having The polycarbonate resin composition of the present invention may contain other resins as long as the effects of the present invention are not impaired.
• the total proportion of the polycarbonate resin (A) and the polycarbonate resin (B) in the polycarbonate resin composition of the present invention is preferably 70% by mass or more, more preferably 100% by mass.
• the mixing ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is 91:9 to 99:1 and 91:9 to 97:3 in mass ratio. is preferred, and 92:8 to 96:4 is more preferred.
• the polycarbonate resin composition of the present invention may contain an antioxidant, a release agent, a processing stabilizer, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, or the like. addition is preferred.
• Antioxidants include hindered phenol antioxidants, phosphite antioxidants, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1, 6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert- Butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-
• the content of the antioxidant in the polycarbonate resin composition is preferably 0.001 to 0.3 parts by mass with respect to the total of 100 parts by mass of the polycarbonate resins (A) and (B).
• the release agent 90% by mass or more of it is preferably an ester of alcohol and fatty acid.
• esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or full esters of polyhydric alcohols and fatty acids.
• the ester of monohydric alcohol and fatty acid an ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms is preferable.
• the partial or full ester of a polyhydric alcohol and a fatty acid a partial or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred.
• esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate.
• Partial or full esters of polyhydric alcohols with saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostea dipentaerythritol, such as dilate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexylstearate, dipentaerythritol
• the content of these releasing agents is preferably in the range of 0.005 to 2.0 parts by mass, and 0.01 to 0.6 parts by mass with respect to the total of 100 parts by mass of the polycarbonate resins (A) and (B).
• a range is more preferable, and a range of 0.02 to 0.5 parts by mass is even more preferable.
• processing stabilizers include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers.
• Phosphorous processing heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.
• triphenylphosphite tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite
• the content of the phosphorus-based processing heat stabilizer in the polycarbonate resin composition is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A) and (B).
• Sulfur-based processing heat stabilizers include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate). , dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and the like.
• the content of the sulfur-based processing heat stabilizer in the polycarbonate resin composition is preferably 0.001 to 0.2 parts by mass with respect to the total of 100 parts by mass of the polycarbonate resins (A) and (B).
• At least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
• Absorbents are preferred. That is, any of the ultraviolet absorbers listed below may be used alone, or two or more thereof may be used in combination.
• Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1,1 ,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy -5-tert-octylpheny
• Benzophenone UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2- methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.
• Triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol and the like.
• Cyclic imino ester UV absorbers include 2,2′-bis(3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis(3,1-benzoxazin-4-one). , 2,2′-m-phenylenebis(3,1-benzoxazin-4-one), 2,2′-(4,4′-diphenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2′-(1,5-naphthalene)bis(3,1-benzoxazin-4-one) ), 2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2′-(2-nitro-p-phenylene)bis(3,1- benzoxazin-4-one) and 2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).
• cyanoacrylate ultraviolet absorber 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenyl acryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like.
• the content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass, more preferably 0.02 to 1.0 parts by mass, with respect to the total 100 parts by mass of the polycarbonate resins (A) and (B). parts by mass, more preferably 0.05 to 0.8 parts by mass. Within such a blending amount range, it is possible to impart sufficient weather resistance to the polycarbonate resin composition depending on the application.
• the polycarbonate resin composition there are impurities such as phenol generated during manufacturing and carbonic acid diesters that remain unreacted.
• the phenol content in the polycarbonate resin composition is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. It is even more preferable to have Also, the carbonic acid diester content in the polycarbonate resin composition is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm.
• the method for producing the polycarbonate resin composition of the present invention is not particularly limited. ) A method of adding a solid polycarbonate resin (B) to a molten polycarbonate resin (A) and kneading them, (3) Adding a solid polycarbonate resin (A) to a molten polycarbonate resin (B) (4) A method of mixing and kneading the polycarbonate resin (A) in a molten state and the polycarbonate resin (B) in a molten state. Kneading may be performed either continuously or batchwise.
• the kneader is preferably an extruder if it is a continuous type, and a Laboplastomill or a kneader if it is a batch type.
• the polycarbonate resin (A) in the present invention can be produced by a melt polycondensation method using a dihydroxy compound represented by the general formula (i) and a diester carbonate as raw materials.
• the isomer ratio is from 50:50 to 80:20.
• the polycondensation catalyst can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both.
• the polycarbonate resin (B) in the present invention can be produced by a melt polycondensation method using a dihydroxy compound represented by the general formula (ii) and a diester carbonate as raw materials.
• Carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like.
• diphenyl carbonate is particularly preferred from the viewpoint of reactivity and purity.
• the carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, per 1 mol of the diol component. By adjusting this molar ratio, the molecular weight of the polycarbonate resin is controlled.
• Examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• alkali metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals.
• alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metal compounds.
• magnesium hydroxide, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like are used.
• nitrogen-containing compounds include quaternary ammonium hydroxides and salts thereof, amines, and the like.
• quaternary ammonium hydroxides having an alkyl or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine , dimethylbenzylamine, tertiary amines such as triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.
• bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate and tetraphenylammonium tetraphenylborate.
• Salts of zinc, tin, zirconium, and lead are preferably used as transesterification catalysts, and these can be used alone or in combination. It may also be used in combination with the alkali metal compound or alkaline earth metal compound described above.
• transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin acetate (II), tin acetate (IV), and dibutyltin.
• Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV) and the like are used.
• These catalysts are preferably used in a ratio of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 3 mol, more preferably 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mol, per 1 mol of the total diol compound. Used in molar proportions.
• melt polycondensation is performed using the raw materials and catalysts described above under heating under normal pressure or reduced pressure while removing by-products through transesterification.
• the reaction is generally carried out in two or more stages.
• the first stage reaction is carried out at a temperature of 120-260°C, preferably 180-240°C, for 0.1-5 hours, preferably 0.5-3 hours.
• the diol compound and the diester carbonate are reacted by raising the reaction temperature while increasing the degree of pressure reduction in the reaction system, and finally polycondensing at a temperature of 200 to 350° C. for 0.05 to 2 hours under a pressure reduction of 1 mmHg or less. carry out the reaction.
• Such reactions may be carried out continuously or batchwise.
• the reactor used for the above reaction may be a vertical type equipped with anchor-type stirring blades, Maxblend stirring blades, helical ribbon-type stirring blades, etc., or may be equipped with paddle blades, lattice blades, spectacle blades, etc. It may be of a horizontal type 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.
• these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
• esters Phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphites such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphoric acid Phosphates such as dioctyl and monooctyl phosphate; Phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid; Phosphonates such as diethyl phenylphosphonate; Tripheny
• butyl p-toluenesulfonate from the viewpoint of the deactivation effect and the hue and stability of the resin.
• These deactivators are preferably used in an amount of 0.01 to 50 times mol, more preferably 0.3 to 20 times mol, relative to the catalyst amount. If it is less than 0.01 times the molar amount of the catalyst, the deactivation effect becomes insufficient, which is not preferred. On the other hand, when the amount is more than 50 times the molar amount of the catalyst, the heat resistance is lowered and the molded article tends to be colored, which is not preferable.
• a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided.
• a horizontal device equipped with stirring blades having excellent surface renewal performance, such as blades, or a thin film evaporator is preferably used.
• the polycarbonate resin composition of the present invention is desired to contain as little foreign matter as possible, and the filtration of the molten raw material and the filtration of the catalyst solution are preferably carried out.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
• filtration of the resulting resin through a polymer filter is preferably carried out.
• the mesh of the polymer filter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
• the step of collecting resin pellets must naturally be in a low-dust environment, preferably class 1000 or less, more preferably class 100 or less.
• the glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is preferably 132-135°C, more preferably 132-133°C.
• the polycarbonate resin composition of the present invention preferably has a refractive index of 1.533 to 1.547, more preferably 1.535 to 1.542, measured by the method of JIS-K-7142 after molding. .
• the polycarbonate resin composition of the present invention preferably has an Abbe number of 46 to 55, more preferably 48 to 53, measured by the method of JIS-K-7142 after molding.
• the polycarbonate resin composition of the present invention has a photoelastic coefficient of 11.0 to 12.0 ( ⁇ 10 ⁇ 12 m 2 /N) measured on a cast film having a thickness of 0.1 mm obtained by molding. is preferably 11.0 to 11.5 ( ⁇ 10 ⁇ 12 m 2 /N).
• the preferred polystyrene equivalent weight average molecular weight (Mw) of the polycarbonate resin composition of the present invention is 20,000 to 70,000.
• a more preferable polystyrene equivalent weight average molecular weight (Mw) is 25,000 to 65,000, and a particularly preferable polystyrene equivalent weight average molecular weight (Mw) is 30,000 to 60,000.
• Mw is less than 20,000, the optical lens becomes fragile, which is not preferable.
• the Mw is more than 70,000, the melt viscosity becomes high, making it difficult to remove the resin after production, and furthermore, the flowability deteriorates, making it difficult to perform injection molding in a molten state, which is not preferable.
• Decahydro-1,4:5,8-dimethanonaphthalenediol (D-NDM) contained in the final pellet (polycarbonate resin composition containing additives) from the viewpoint of yellowing resistance and stability (heat resistance, weather resistance, etc.) is preferably 30 ppm or less, more preferably 20 ppm or less.
• the optical lens of the present invention can be obtained by injection molding the above polycarbonate resin composition of the present invention into a lens shape using an injection molding machine or an injection compression molding machine. Molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 280°C. Also, 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 naturally be a low-dust environment, preferably class 1000 or less, more preferably class 100 or less.
• the optical lens of the present invention is preferably used in the form of an aspherical lens if necessary.
• Aspherical lenses can eliminate spherical aberration with a single lens, so there is no need to combine multiple spherical lenses to remove spherical aberration, which helps reduce weight and production costs. be possible. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.
• the astigmatism of the aspheric 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 depending on the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm.
• a coat 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, if necessary.
• the antireflection layer may be a single layer or multiple layers, and may be organic or inorganic, but is preferably inorganic. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride are exemplified.
• the antireflection layer although there are no particular limitations on the combination of single layer/multilayer, the combination of their components and thickness, etc., a two-layer structure or a three-layer structure is preferred, and a three-layer structure is particularly preferred.
• the antireflection layer as a whole is preferably formed to a thickness of 0.00017 to 3.3%, specifically 0.05 to 3 ⁇ m, particularly preferably 1 to 2 ⁇ m, of the thickness of the optical lens. .
• Refractive index (nD) A cast film having a thickness of 0.1 mm obtained by molding the obtained polycarbonate resin composition was measured using an Abbe refractometer according to JIS-K-7142.
• Tg Glass transition temperature
• DSC differential scanning calorimeter
• Photoelastic coefficient A cast film having a thickness of 0.1 mm obtained by molding the obtained polycarbonate resin composition was measured using an ellipsometer to measure changes in birefringence with respect to changes in load at a wavelength of 633 nm. bottom. Ellipsometer: M-220 manufactured by JASCO Corporation
• the temperature was lowered to 1 Torr or less over 40 minutes, and the polymerization reaction was carried out under the conditions of 240° C. and 1 Torr or less with stirring for 10 minutes. After completion of the reaction, nitrogen was blown into the reactor to pressurize it, and the polycarbonate resin (D-NDM-PC) produced was withdrawn while being pelletized.
• D-NDM-PC polycarbonate resin
• Example 1 2881 g of the polycarbonate resin (D-NDM-PC) obtained in Synthesis Example 1 (13.0 mol in terms of D-NDM monomer units) and 119 g of the polycarbonate resin (BPEF-PC) obtained in Synthesis Example 2 (BPEF monomer 0.27 mol in terms of units), 3.0 g of a hindered phenol antioxidant (AO-60 manufactured by ADEKA Co., Ltd.), and a phosphite antioxidant (PEP-36 manufactured by ADEKA Co., Ltd.).
• D-NDM-PC polycarbonate resin obtained in Synthesis Example 1
• BPEF-PC polycarbonate resin obtained in Synthesis Example 2
• BPEF monomer 0.27 mol in terms of units 3.0 g of a hindered phenol antioxidant (AO-60 manufactured by ADEKA Co., Ltd.), and a phosphite antioxidant (PEP-36 manufactured by ADEKA Co., Ltd.).
• Example 2 Comparative Examples 1 to 3
• a polycarbonate resin composition was obtained in the same manner as in Example 1, except that the polycarbonate resin (D-NDM-PC and/or BPEF-PC) shown in Table 1 was used instead of the polycarbonate resin used in Example 1.
• Table 1 shows the physical properties of the obtained polycarbonate resin composition.
• a polycarbonate resin composition was obtained in the same manner as in Example 1, except that 3000 g of the polycarbonate resin (BPEF-TCDDM-PC) obtained above was used instead of the polycarbonate resin used in Example 1.
• Table 1 shows the physical properties of the obtained polycarbonate resin composition.
• the polycarbonate resin composition of the present invention can be suitably used as a camera lens for smartphones, DSCs, in-vehicle cameras, and the like. Furthermore, the use of the polycarbonate resin composition of the present invention can be expected to reduce the thickness of lens units used for telephoto applications.

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• 2022
  • 2022-11-28 KR KR1020247009215A patent/KR20240112253A/ko active Pending
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