Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/04—Particle-shaped
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • 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
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
• • 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
  • G02B1/045—Light guides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/527—Cyclic esters
• • 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
• • 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
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • 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
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

• the present invention relates to a polycarbonate resin composition pellet and a manufacturing method thereof, and more particularly to a polycarbonate resin composition pellet used as a raw material for an optical member such as a light guide plate of a liquid crystal backlight unit and a manufacturing method thereof.
• PC polycarbonate resin or a resin composition
• a light guide member of a small liquid crystal display from the viewpoint of heat resistance and mechanical strength (see, for example, Patent Document 1). ).
• PC is granulated into pellets by extrusion granulation at 240 to 270 ° C., and the pellets are molded into various members by injection molding or extrusion molding.
• the light guide member using PC since the light tends to become yellow in the anti-light-incident part, it is difficult to obtain a uniform color tone of the screen. It has become.
• Various attempts have been made to improve the light transmittance in the short wavelength region of PC, but it has not been sufficient yet and has not been at a level sufficient for practical use.
• the problem to be solved by the present invention is to provide a polycarbonate resin composition pellet having high light transmittance in a short wavelength region and excellent color tone uniformity when molded into a light guide member.
• the present inventors have found that the light transmittance in the short wavelength region of the polycarbonate resin composition is greatly influenced by the thermal history during kneading and molding of the polycarbonate resin composition.
• the present invention has been completed based on such findings.
• the present invention provides the following polycarbonate resin composition pellets and a method for producing the same.
• a methylene chloride solution having a concentration of 12 g / dL was placed in a quartz glass cell having an optical path length of 5 cm and the light transmittance was measured, the light transmittance at a wavelength of 380 nm was 97.0% or more, and the viscosity average molecular weight (Mv ) In the range of 11,000 to 22,000.
• ⁇ 2> Shear applied to the resin by the ratio Q / Ns between the resin supply amount Q (kg / h) of the kneading machine and the screw rotation speed Ns (rpm) of the kneading machine used when producing the pellets
• the polycarbonate resin composition pellets according to the above ⁇ 1> which are produced by controlling to a suitable range from the balance.
• the phosphite represented by the general formula (I-1) is a compound represented by the following general formula (I-2), according to any one of the above ⁇ 1> to ⁇ 3> Polycarbonate resin composition pellets.
• R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 and R 12 each independently represents a hydrogen atom or an alkyl group
• R 4 , R 7 , R 10 and R 13 each independently represents an alkyl group, an aryl group or an aralkyl group
• m1 to m4 each independently represents an integer of 0 to 3.
• the resin component of the polycarbonate resin composition has repeating units represented by the following general formulas (III) and (IV), respectively, and the content of the repeating unit represented by the following general formula (IV) is 1
• X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO- , —SO 2 —, —O—, —CO—, or a bond represented by the following formula (V-1) or (V-2).
• R 23 and R 24 each independently represents an alkyl group having 1 to 3 carbon atoms
• Y represents a linear or branched alkylene group having 2 to 15 carbon atoms.
• a to d are each independently an integer of 0 to 4, and p is an integer of 2 to 200.
• a method of manufacturing comprising: The ratio Q / Ns between the resin supply amount Q (kg / h) of the kneading machine and the screw rotation speed Ns (rpm) of the kneading machine is controlled within a range that suppresses the deterioration of the color tone due to the heat history during melt kneading.
• a method for producing a pellet of a polycarbonate resin composition wherein the polycarbonate resin composition is kneaded and granulated.
• the solution transmittance at a wavelength of 380 nm of the polycarbonate resin composition before granulation into pellets is 98.0% or more, and the decrease in transmittance in the kneading granulation step is 1.0% or less.
• the polycarbonate resin composition pellets of the present invention have little yellowness and high light transmittance in a short wavelength region without containing additives such as bluing agents.
• a light guide member having excellent color tone uniformity can be provided.
• the polycarbonate resin composition pellet which has the high light transmittance in a short wavelength range and which has the outstanding color tone can be provided.
• the polycarbonate resin composition pellets of the present invention had a light transmittance of 97.0% or more at a wavelength of 380 nm when a methylene chloride solution having a concentration of 12 g / dL was placed in a quartz glass cell having an optical path length of 5 cm and the light transmittance was measured.
• the viscosity average molecular weight (Mv) is in the range of 11,000 to 22,000.
• the measurement of the transmittance of a resin or a resin composition is often performed using an injection molded product.
• the light transmittance in the short wavelength region of the polycarbonate resin composition is greatly influenced by the thermal history during kneading and molding of the polycarbonate resin composition. That is, thermal degradation may occur when molding into an injection molded product, and the light transmittance may be affected by another factor such as molding strain. Therefore, it is necessary to quantitatively evaluate the transmittance of the polycarbonate resin composition itself by a method that does not receive thermal history.
• a polycarbonate resin composition is dissolved in methylene chloride to prepare a 12 g / dL methylene chloride solution, which is put into a quartz glass cell having an optical path length of 5 cm (width 1 cm), and light transmittance is measured. To do. Thereby, it is possible to evaluate the resin composition before granulation into pellets and the optical characteristics of the pellets by excluding molding factors.
• the light transmittance in wavelength 380nm is measured as a light transmittance in a short wavelength region from a viewpoint of evaluating the color difference of the light incident part / anti-light incident part in a light guide member.
• the light transmittance in the present invention is measured according to the following method.
• the measurement cell should be thoroughly cleaned and careful attention should be paid to the measurement environment so that dust does not enter.
• a deuterium lamp is used for wavelengths of 300 to 359 nm
• a halogen lamp is used for wavelengths of 360 to 800 nm.
• the light transmittance of PC for light guide members is generally not changed even if the light guide performance of the pellet is changed in the middle to high wavelength range of visible light of 500 to 800 nm, but the color tone of the pellet is short wavelength range of 500 nm or less. Reflect.
• the light transmittance at 380 nm, the shortest wavelength of visible light, which easily reflects the difference in transmittance among samples, is selected and used as an index of light guide characteristics.
• the concentration of the solution When the concentration of the solution is higher than 12 g / dL, a significant difference in color tone between samples can be detected. However, since the concentration unevenness due to volatilization of methylene chloride in the solution is likely to occur, measurement stability is poor and the cell A long standing time is required after pouring the solution. On the other hand, when the concentration of the solution is lower than 12 g / dL, although it is difficult to generate density unevenness that is a factor that makes measurement unstable, stable measurement can be performed, but a significant difference in color tone between samples that can be found by measurement is small. . For this reason, the density
• the polycarbonate resin composition pellet of the present invention has a light transmittance of 97.0% or more, preferably 97.5% or more, more preferably 97.8, measured at the wavelength of 380 nm measured by the above method. % Or more, more preferably 98.0% or more. From the viewpoint of color tone, the higher the light transmittance, the better, and the upper limit is not particularly limited.
• the polycarbonate resin composition in the present invention preferably contains at least one component selected from the group consisting of the following components (A) to (F) with respect to 100 parts by mass of the resin component.
• the organopolysiloxane compound of the component (A) is a reactive silicone compound having at least one functional group among a phenyl group, an alkoxy group and a vinyl group in the silicone compound.
• the organopolysiloxane compound may be any compound having at least one functional group selected from a phenyl group, an alkoxy group, and a vinyl group. Among them, a compound having a kinematic viscosity at 25 ° C. of about 1 to 500 cSt is preferable.
• This component (A) is a compound that acts as a stabilizer in a PC-based resin.
• component (A) By blending the component (A), yellowing due to thermal deterioration during molding, poor appearance such as silver (silver strip), bubbles, etc. Mixing can be prevented.
• organopolysiloxane compound having at least one functional group of phenyl group, alkoxy group, and vinyl group are commercially available products KR-511 and KR-9218 (both manufactured by Shin-Etsu Chemical Co., Ltd., trade names) ) Can be used, but is not limited thereto.
• the amount of component (A) is preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.2 parts by mass, with respect to 100 parts by mass of the resin component. When the amount is too small, the effect as a stabilizer is insufficient, and when the amount is too large, fogging occurs.
• the phosphite ester of the component (B) is a phosphite ester represented by the general formula (I-1) and is a compound that acts as an antioxidant.
• the alkyl group represented by R 1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
• R 1 is preferably an aryl group represented by any of the following general formulas (Ia), (Ib), or (Ic).
• R 1a represents an alkyl group having 1 to 10 carbon atoms.
• R 1b represents an alkyl group having 1 to 10 carbon atoms.
• the phosphite ester represented by the general formula (I-1) is preferably a compound represented by the following general formula (I-2).
• R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 and R 12 each independently represent a hydrogen atom or an alkyl group
• R 4 , R 7 , R 10 and R 13 each independently represents an alkyl group, an aryl group or an aralkyl group
• m1 to m4 each independently represents an integer of 0 to 3.
• R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 and R 12 are preferably methyl groups, and m1 to m4 are preferably 0.
• the phosphite ester of the component (B) commercially available ADK STAB PEP36, ADK STAB PEP-8 (all are manufactured by ADEKA, trade name), Weston 618, Weston 619G (all above, both are GE) And Doverphos S-9228PC (manufactured by Dover Chemical, trade name), but is not limited thereto.
• the amount of component (B) is preferably 0.01 to 0.10 parts by mass, more preferably 0.03 to 0.08 parts by mass, with respect to 100 parts by mass of the resin component. If the amount is too small, the antioxidant effect is insufficient, and if the amount is too large, no improvement in the antioxidant effect is recognized.
• the release agent for the component (C) is at least one selected from fatty acid monoglycerides having 16 to 30 carbon atoms. Specific examples of the fatty acid monoglyceride having 16 to 30 carbon atoms include stearic acid monoglyceride. Fatty acid monoglyceride is preferably used as the release agent since it has charging properties in addition to releasability, but fatty acid full esters can also be used.
• the amount of component (C) is preferably 0.01 to 0.10 parts by mass, more preferably 0.03 to 0.05 parts by mass, with respect to 100 parts by mass of the resin component. When the amount is too small, the releasability is not sufficiently exhibited, and when the amount is too large, the color tone stability at high temperature molding is lowered.
• the (D) component polyoxytetramethylene polyoxyethylene glycol is a compound represented by the general formula (II).
• m and n each independently represent an integer of 4 to 60, and m + n is an integer of 20 to 90.
• m is 10 to 40, n is 10 to 40, and m + n is 20 to 80. More preferably, m is 15 to 35, n is 15 to 35, and m + n is 30 to 70.
• the blending amount of component (D) is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 1.2 parts by mass with respect to 100 parts by mass of the resin component, from the viewpoint of the effect of improving the color tone.
• the alicyclic epoxy compound of the above component (E) refers to a cycloaliphatic compound having an alicyclic epoxy group, that is, an epoxy group in which one oxygen atom is added to an ethylene bond in the aliphatic ring.
• a cycloaliphatic compound having an alicyclic epoxy group that is, an epoxy group in which one oxygen atom is added to an ethylene bond in the aliphatic ring.
• those represented by the following formulas (1) to (10) disclosed in JP-A-11-158364 are preferably used.
• the compound represented by the formula (1), the formula (7) or the formula (10) is superior in compatibility with the PC resin and does not impair the transparency.
• the compound represented by the formula (1), the formula (7) or the formula (10) is superior in compatibility with the PC resin and does not impair the transparency.
• the compounding amount of the alicyclic epoxy compound as the component (E) is 0.01 to 0.03 parts by mass with respect to 100 parts by mass of the resin component.
• the component (F) acrylic resin refers to a polymer having a repeating unit of at least one selected from monomer units of acrylic acid, acrylic ester, acrylonitrile and derivatives thereof. It refers to a copolymer. Specifically, polyacrylic acid, polymethyl methacrylate (PMMA), polyacrylonitrile, ethyl acrylate-acrylic acid-2-chloroethyl copolymer, acrylic acid-n-butyl-acrylonitrile copolymer, acrylonitrile-styrene copolymer And acrylonitrile-butadiene copolymer and acrylonitrile-butadiene-styrene copolymer.
• PMMA polymethyl methacrylate
• PMMA polyacrylonitrile
• ethyl acrylate-acrylic acid-2-chloroethyl copolymer acrylic acid-n-butyl-acrylonitrile copolymer
• polymethyl methacrylate (PMMA) can be particularly preferably used.
• the component (F) acrylic resin requires a molecular weight of 200 to 100,000, preferably 20,000 to 60,000. When the molecular weight is 200 to 100,000, the phase separation between the PC copolymer and other PC resins and the acrylic resin does not become too fast during molding, so that sufficient transparency can be obtained in the molded product. It is done.
• polymethyl methacrylate (PMMA) known ones can be used. Usually, those produced by bulk polymerization of methyl methacrylate monomers in the presence of a peroxide or azo polymerization initiator are used. preferable.
• the amount of component (F) is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, and still more preferably 0.1 to 0.3 part by weight based on 100 parts by weight of the resin component. Part by mass.
• the blending amount of the acrylic resin is 0.01 parts by mass or more, the transparency of the molded product is improved, and when it is 1 part by mass or less, the transparency can be maintained without impairing other desired physical properties. .
• the resin component of the polycarbonate resin composition in the present invention may be a single polycarbonate resin or a mixture of two or more kinds of polycarbonate resins.
• the polycarbonate resin is not particularly limited, but bisphenol A polycarbonate resin using bisphenol A as a raw material is preferable.
• the polycarbonate resin may be a copolymer, and has a repeating unit represented by the following general formulas (III) and (IV) from the viewpoint of color tone, and is represented by the following general formula (IV).
• a phenol-modified diol-copolymerized polycarbonate having a repeating unit content of 1 to 10% by mass can be used.
• R 21 and R 22 each independently represents an alkyl group having 1 to 6 carbon atoms.
• X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO- , —SO 2 —, —O—, —CO—, or a bond represented by the following formula (V-1) or (V-2).
• R 23 and R 24 each independently represents an alkyl group having 1 to 3 carbon atoms
• Y represents a linear or branched alkylene group having 2 to 15 carbon atoms.
• a to d are each independently an integer of 0 to 4, and p is an integer of 2 to 200.
• the copolymer can be obtained by copolymerizing a dihydric phenol and a phenol-modified diol, which will be described later, by an interfacial polymerization method. Specifically, for example, in an inert solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, a catalyst or a branching agent is added as necessary, and dihydric phenol, phenol-modified diol and phosgene are added. A carbonate precursor such as is reacted.
• dihydric phenol examples include compounds represented by the following general formula (III-a).
• R 21 and R 22 each independently represents an alkyl group having 1 to 6 carbon atoms.
• the alkyl group may be linear, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, and isohexyl group. , Cyclopentyl group, cyclohexyl group and the like.
• a and b represent the number of substitutions of R 21 and R 22 , respectively, and are integers from 0 to 4.
• R 21 may be the same or different from each other, if R 22 is plural, R 22 may be the same or different from each other.
• X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or a carbon number. 5 to 15 cycloalkylidene groups, —S—, —SO—, —SO 2 —, —O—, —CO— or a bond represented by the above formula (V-1) or (V-2) is represented.
• Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylylene group, and hexylene group.
• Examples of the alkylidene group having 2 to 8 carbon atoms include an ethylidene group and an isopropylidene group.
• Examples of the cycloalkylene group having 5 to 15 carbon atoms include a cyclopentylene group and a cyclohexylene group.
• Examples of the cycloalkylidene group having 5 to 15 carbon atoms include a cyclopentylidene group and a cyclohexylidene group.
• bisphenol A 2,2-bis (4-hydroxyphenyl) propane
• bisphenols other than bisphenol A include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, and dihydroxydiphenyls.
• Dihydroxydiarylfluorenes dihydroxydiaryladamantanes, bis (4-hydroxyphenyl) diphenylmethane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxy Phenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene, ⁇ , ⁇ -bishydroxyphenyl polydi Chill siloxane compounds.
• bis (hydroxyaryl) alkanes include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; 2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; bis (4-hydroxyphenyl) naphthyl 1,2-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5- Tetramethylphenyl) propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydride) Carboxy-3,5-tetramethylene-chlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane.
• bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxy Phenyl) -3,5,5-trimethylcyclohexane; 2,2′-bis (4-hydroxyphenyl) norbornene and the like.
• dihydroxyaryl ethers include 4,4′-dihydroxyphenyl ether; 4,4′-dihydroxy-3,3′-dimethylphenyl ether and the like.
• dihydroxydiaryl sulfides include 4,4′-dihydroxydiphenyl sulfide; 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide.
• dihydroxydiaryl sulfoxides include 4,4′-dihydroxydiphenyl sulfoxide; 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide and the like.
• dihydroxydiaryl sulfones include 4,4′-dihydroxydiphenyl sulfone; 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone and the like.
• dihydroxydiphenyls include 4,4′-dihydroxydiphenyl.
• dihydroxydiarylfluorenes include 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.
• dihydroxydiaryladamantanes include bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane; 2,2-bis (4-hydroxyphenyl) adamantane; 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like. These dihydric phenols may be used alone or in combination of two or more.
• phenol-modified diol examples include compounds represented by the following general formula (IV-a).
• R 23 and R 24 each independently represents an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. It is done. c and d represent the number of substitutions of R 23 and R 24 , respectively, and are integers from 0 to 4. In the case where R 23 is more or different and a plurality of R 23 are identical to one another, if R 24 is plural, R 24 may be the same or different from each other.
• Y represents a linear or branched alkylene group having 2 to 15 carbon atoms.
• the linear or branched alkylene group having 2 to 15 carbon atoms include alkylene groups such as ethylene group, propylene group, butylene group, isobutylene group, pentylene group and isopentylene group, ethylidene group, propylidene group, isopropylidene group, butylidene And alkylidene residues such as a group, isobutylidene group, pentylidene group and isopentylidene group.
• p is an integer of 2 to 200, preferably 6 to 70.
• the phenol-modified diol represented by the above general formula (IV-a) is a compound derived from hydroxybenzoic acid or its alkyl ester, acid chloride and polyether diol.
• Phenol-modified diols can be synthesized by methods proposed in JP-A-62-79222, JP-A-60-79072, JP-A-2002-173465, and the like. It is desirable to appropriately purify the phenol-modified diol obtained.
• the purification method for example, the system is depressurized after the reaction, and excess raw material (for example, parahydroxybenzoic acid) is distilled off.
• the phenol-modified diol is washed with water or an aqueous alkaline solution (for example, sodium bicarbonate aqueous solution). The method of doing is desirable.
• the hydroxybenzoic acid alkyl ester include hydroxybenzoic acid methyl ester and hydroxybenzoic acid ethyl ester.
• the polyether diol is represented by HO— (Y—O) p —H, and consists of repeating linear or branched alkyl ethers having 2 to 15 carbon atoms. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polytetramethylene glycol is particularly preferable from the viewpoints of availability and hydrophobicity. It is preferable that the repeating number p of the ether part of the polyether diol is 2 to 200, preferably 6 to 70.
• acid chlorides are those obtained from hydroxybenzoic acid and phosgene. More specifically, it can be obtained by the method described in Japanese Patent No. 2652707.
• Hydroxybenzoic acid or an alkyl ester thereof may be any of a para isomer, a meta isomer, and an ortho isomer, but the para isomer is preferable from the viewpoint of copolymerization.
• Ortho forms may be inferior in copolymerization reactivity due to steric hindrance to hydroxyl groups.
• the phenol-modified diol is preferably used as a methylene chloride solution as much as possible in order to prevent its alteration and the like.
• it cannot be used as a methylene chloride solution, it can be used as an alkaline aqueous solution such as NaOH.
• the copolymerization amount of the phenol-modified diol is preferably selected according to the desired balance between fluidity and heat resistance.
• the amount of phenol-modified diol copolymerization exceeds 40% by mass, it becomes elastomeric as disclosed in JP-A-62-79222, and there is a possibility that it cannot be applied to the same use as a general PC resin.
• the amount of the phenol-modified diol residue contained in the PC copolymer is required to be 1 to 30% by mass in the present invention, and preferably 1 to 20% by mass. %, More preferably 1 to 15% by mass.
• any molecular weight regulator may be used as long as it is usually used for polymerization of PC resins.
• monohydric phenol for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol
• a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt, or the like can be preferably used.
• the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like, and examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Etc.
• Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide.
• Examples thereof include butylphosphonium chloride and tetrabutylphosphonium bromide.
• These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferable, and triethylamine is particularly preferable.
• inert organic solvents there are various kinds of inert organic solvents.
• dichloromethane methylene chloride
• trichloromethane carbon tetrachloride
• 1,1-dichloroethane 1,2-dichloroethane
• 1,1,1-trichloroethane 1,1,2-trichloroethane
• -Tetrachloroethane 1,1,2,2-tetrachloroethane
• pentachloroethane chlorinated hydrocarbons such as chlorobenzene, toluene, acetophenone, and the like.
• organic solvents may be used alone or in combination of two or more.
• methylene chloride is particularly preferred.
• a compound having three or more functional groups such as [ ⁇ ′, ⁇ ′-bis (4 ′′ -hydroxyphenyl) ethyl] benzene; phloroglysin, trimellitic acid, and isatin bis (o-cresol) can also be used.
• the blending amount of the copolymer in the resin component is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 20% by mass with respect to 100% by mass of the resin component, from the viewpoint of the effect of improving the color tone. 50% by mass.
• various additives may be added to the polycarbonate resin composition as necessary within the range not impairing the effects of the present invention.
• the various additives include phosphorous antioxidants other than the component (B), phenolic antioxidants, ultraviolet absorbers such as benzotriazoles and benzophenones, light stabilizers such as hindered amines, and aliphatic carboxyls.
• examples thereof include internal lubricants such as acid ester compounds, paraffin compounds, silicone oil, and polyethylene wax, conventional flame retardants, flame retardant aids, mold release agents, antistatic agents, and colorants.
• the blending amount of these components is appropriately determined within a range not impairing the effects of the present invention. For example, it is about 0.01 to 1 part by mass, preferably 0.05 to 100 parts by mass of the resin component. Is 0.3 parts by mass, more preferably 0.1-0.3 parts by mass.
• Examples of phosphorus antioxidants other than the component (B) include triphenyl phosphite, diphenylnonyl phosphite, diphenyl (2-ethylhexyl) phosphite, and tris (2,4-di-t-butylphenyl) phosphine.
• Examples of the phosphorus-based antioxidant other than the component (B) include Irgafos 168, Irgafos 12, Irgafos 38 (all of which are manufactured by BASF, trade names), ADK STAB C, ADK STAB 329K (all of which are manufactured by ADEKA Corporation). , Trade name), JC263 (made by Johoku Chemical Industry Co., Ltd., trade name), Sardstab P-EPQ (made by Clariant, trade name) and Weston 624 (made by GE, trade name). it can.
• phenolic antioxidant examples include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2 Hindered phenols such as 2,2'-methylenebis (4-methyl-6-tert-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Can be mentioned.
• phenolic antioxidants examples include Irganox 1010, Irganox 1076, Irganox 1330, Irganox 3114, Irganox 3125 (all of which are manufactured by BASF, trade name), BHT (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), and Cyanod 1790 (Syanamid 1790). And commercial products such as Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
• the ratio Q / Ns between the resin supply amount Q (kg / h) of the kneading machine used when producing the pellets and the screw rotation speed Ns (rpm) of the kneading machine is added to the residence time and the resin.
• Q / Ns varies greatly depending on the output of the extruder used, the screw diameter, the screw dimensions, temperature conditions, and the discharge amount. Can not.
• Screw length / screw diameter (L / D) 31.5 in a twin-screw kneader (trade name “TEX65 ⁇ II”, manufactured by Nippon Steel Works) (2) Using a single screw having a layout such as wide full flight, full flight, neutral, etc. (3) Cylinder to die temperature is set to 220 ° C to 270 ° C, (4) Strands were formed at a discharge rate of 800 to 1000 kg / hr, and pellets were granulated. The solution permeability of the polycarbonate flakes provided to the raw material and the solution permeability of the obtained pellets were measured and the difference was calculated. The solution permeability of the pellets decreased as the thermal history received by the pellets increased.
• the Q / Ns range (1.85) in which the decrease in the solution permeability of flakes and pellets was minimized while the YY of the 3 mm-thick plate was finally reduced while changing the screw rotation speed Ns.
• the Q / Ns range (1.85) in which the decrease in the solution permeability of flakes and pellets was minimized while the YY of the 3 mm-thick plate was finally reduced while changing the screw rotation speed Ns.
• the Q / Ns is controlled to 1.85 to 1.95, it cannot be applied to all extruders.
• the color tone is measured by molding a plate having a constant thickness, for example, 3 mm.
• the flake color tone measured in this way has already undergone a thermal history during plate molding.
• the color tone of the pellets also received a thermal history during plate molding in addition to a thermal history during pellet granulation.
• This method cannot eliminate the heat history during plate forming. Therefore, in the present invention, a solution permeability measurement method was devised to optimize the extrusion conditions so as to minimize the thermal history of pellet granulation while eliminating the thermal history due to plate molding.
• the solution transmittance at a wavelength of 380 nm of the polycarbonate resin composition before granulation into pellets Is preferably 98.0% or more, and kneading is preferably performed under such a condition that the decrease in transmittance in the kneading granulation step is 1.0% or less.
• the light transmittance of pure methylene chloride was also measured, and this value was used as a reference with a light transmittance of 100%.
• a deuterium lamp is used for wavelengths of 300 to 359 nm
• a halogen lamp is used for wavelengths of 360 to 800 nm.
• the light transmittance of PC for light guide members is generally not changed even if the light guide performance of the pellet is changed in the middle to high wavelength range of visible light of 500 to 800 nm, but the color tone of the pellet is short wavelength range of 500 nm or less. Reflect.
• the light transmittance at 380 nm the shortest wavelength of visible light, which easily reflects the difference in transmittance among samples, is selected and used as an index of light guide characteristics.
• the measurement is preferably performed at 25 ° C. or lower. From the same point of view, the measurement cell should be thoroughly cleaned and careful attention should be paid to the measurement environment so that dust does not enter.
• the LED light source was incident from the end face of a light guide plate having a diagonal length of 2.5 inches and a thickness of 0.4 mm formed at 340 ° C. using PC pellets to emit light.
• x in the XYZ color system at positions 1/8 and 7/8 from the end face of the light incident part (referred to as light incident part and anti-light incident part, respectively).
• the chromaticity and y chromaticity were measured, respectively, and the difference between the light incident part and the counter light incident part of x chromaticity and y chromaticity was measured.
• Bisphenol A Carbonate resin, viscosity average molecular weight (Mv) 23,500, Idemitsu Kosan Co., Ltd.
• B-1 Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, trade name “ADK STAB PEP36”, manufactured by ADEKA Corporation
• B-2 Bis (2,4-dic (Milphenyl) pentaerythritol diphosphite, trade name “Doverphos S-9228PC”, manufactured by Dover Chemical
• G-1 Tris (2,4-di-t-butylphenyl) phosphite, phosphorus antioxidant, trade name “Irgaphos 168”, manufactured by BASF
• Example 3 a light-guide plate was produced and the difference between the light-incidence part and anti-light-incidence part of x chromaticity and y chromaticity in a light guide plate was evaluated. .
• the results are shown in Table 2.
• the color tone of the pellet becomes the best by controlling Q / Ns to 1.85 to 1.95.
• the Q / Ns value deviates from this value, the solution transmittance in the short wavelength region and the injection plate YI decrease.
• the smaller the Mv the higher the solution transmittance at 380 nm. It is high and it can be seen that the color tone is excellent. This is presumably because the smaller the Mv, the lower the temperature setting of the extruder from the viewpoint of fluidity, so that the heat history applied to the resin during kneading can be reduced and the decrease in color tone is suppressed.
• the mechanical strength is better as the molecular weight is higher.
• the x chromaticity difference is as high as 2.9% and the y chromaticity difference is as high as 3.1%, whereas in Examples 3, 12 and 13, the x chromaticity difference is high.
• the chromaticity difference is suppressed to 1.3 to 1.6%, and the y chromaticity difference is suppressed to 1.2 to 1.8%. Therefore, it turns out that the light guide member excellent in color tone uniformity can be provided regardless of the position from the light source by molding the light guide member using the pellet of the present invention.
• the polycarbonate resin composition pellet of the present invention has little yellowness without containing an additive such as a bluing agent, has a high light transmittance in a short wavelength region, and is a raw material for optical members such as a light guide plate of a liquid crystal backlight unit. As useful.

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