Classifications

• • 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
  • C08K5/50—Phosphorus bound to carbon only
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

• the present invention relates to a polycarbonate resin composition and a molded article thereof. More specifically, the present invention relates to a polycarbonate resin composition and a molded article thereof in which the thermal stability is improved by adding a triarylphosphine having a specific structure.
• Polycarbonate resin has excellent heat resistance, mechanical properties, impact resistance, and dimensional stability, and is widely used in applications such as office equipment, automobiles, and electrical and electronic parts.
• issues such as the consumption of limited resources and environmental issues caused by carbon dioxide emissions have come into focus, and there is a demand for polycarbonate resin products with longer product life.
• polycarbonate resin has the problem that it turns yellow and its color deteriorates when exposed to high-temperature environments for long periods of time.
• Patent Document 1 discloses that a polycarbonate resin composition using a phosphine compound in combination with a specific hindered phenol compound suppresses discoloration of the polycarbonate resin in a high-temperature environment, but it shows that the effect of the phosphine compound alone is insufficient, and there is no example of the phosphine compound of the specific structure of the present invention.
• Patent Document 2 discloses that a polycarbonate resin composition using an aryl phosphine compound in combination with an alicyclic epoxy compound suppresses discoloration of the polycarbonate resin in a high-temperature environment, but it shows that the effect of the phosphine compound alone is insufficient, and there is no example of the phosphine compound of the specific structure of the present invention.
• Patent Document 3 discloses that a polycarbonate resin composition using a phosphine compound in combination with a metal boride suppresses discoloration of the polycarbonate resin in a high-temperature environment, but it does not show the effect of the phosphine compound alone. And there is no example of the phosphine compound of the specific structure of the present invention.
• the object of the present invention is to provide a polycarbonate resin composition that is less susceptible to discoloration and has excellent thermal stability, and to provide a molded article obtained by molding the same, in response to the problem of discoloration of polycarbonate resin compositions when exposed to high-temperature environments for long periods of time, as described above.
• a polycarbonate resin composition comprising (A) a polycarbonate resin (component A) and (B) a triarylphosphine (component B) represented by the following formula [1]:
• R 2-1 , R 2-2 , R 2-3 , R 6-1 , R 6-2 , R 6-3 , R 0-1 , R 0-2 and R 0-3 are hydrogen atoms, hydrocarbon groups, alkoxy groups or halogens and may be the same or different, provided that at least one of R 2-1 , R 2-2 , R 2-3 , R 6-1 , R 6-2 and R 6-3 is a hydrocarbon group, alkoxy group or halogen.
• p, q and r are each integers from 0 to 3.
• the polycarbonate resin composition according to the above (1) wherein the triarylphosphine of the component B is tri(o-tolyl)phosphine, tri(2,5-xylyl)phosphine or tri(2,4-xylyl)phosphine.
• the polycarbonate resin composition according to the above item (1) which contains 0.001 to 0.1 part by mass of component B per 100 parts by mass of component A.
• the polycarbonate resin composition of the present invention shows little discoloration even when exposed to high-temperature environments for long periods of time and has excellent thermal stability. Therefore, molded articles made from the polycarbonate resin composition can be suitably used in a variety of industrial applications, including LED lighting and other lighting applications, office automation equipment, electrical and electronic equipment, automobiles, and building materials, and are of great industrial value.
• the polycarbonate resin used as component A of the present invention is usually one obtained by reacting a dihydroxy compound with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or one obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method, or one obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
• the dihydroxy component used here may be any dihydroxy component that is normally used in polycarbonate resins, and may be a bisphenol or an aliphatic diol.
• bisphenols include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, and 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane.
• R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
• R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms;
• p and q are each an integer of 1 to 4, e is a natural number, f is 0 or a natural number, and e+f is a natural number less than 100; and
• X is a divalent aliphatic group having 2 to 8 carbon atoms.
• Aliphatic diols include, for example, 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis(2-hydroxyethoxy)biphenyl, bis ⁇ (2-hydroxyethoxy)phenyl ⁇ methane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ ethane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ -1-phenylethane, 2,2-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ propane, 2,2-bis ⁇ (2-hydroxyethoxy)-3-methylphenyl ⁇ propane, 1,1-bis(2-hydroxyethoxy)phenyl ⁇ -3,3,5-trimethylcyclohexane, 2,2-bis ⁇ 4-(2-hydroxyethoxy)phenyl ⁇ methane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇
• aromatic bisphenols are preferred, particularly 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3 -methylphenyl)fluorene, 1,3-bis ⁇ 2-(4-hydroxyphenyl)propyl ⁇ benzene, and 1,4-bis ⁇ 2-(4-hydroxyphenyl)propyl ⁇ benzene, and the bisphenol compound represented by the above formula [6] are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)propan
• the polycarbonate resin used as component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound.
• Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4- ⁇ 4-[1,1-bis(4-hydroxyphenyl)-2,4-dihydroxyphenyl)ethane ...
• Examples include trisphenols such as ⁇ 4-hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.
• trisphenols such as ⁇ 4-hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy
• polycarbonate resins are produced by known reaction methods for producing ordinary aromatic polycarbonate resins, for example, by reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or a carbonic acid diester.
• a carbonate precursor such as phosgene or a carbonic acid diester.
• the reaction is usually carried out in the presence of an acid binder and a solvent.
• an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
• the solvent for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used.
• a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction.
• the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
• an ester exchange reaction using a carbonic acid diester as a carbonate precursor a predetermined ratio of aromatic dihydroxy components is stirred with the carbonic acid diester while heating in an inert gas atmosphere, and the resulting alcohol or phenol is distilled off.
• the reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C.
• the reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol.
• a catalyst usually used in ester exchange reactions can be used to promote the reaction.
• Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
• a terminal terminator is used in the polymerization reaction.
• the terminal terminator is used to adjust the molecular weight, and the resulting polycarbonate resin has excellent thermal stability compared to those that are not terminated, since the ends are blocked.
• Examples of such terminal terminators include monofunctional phenols represented by the following formulas [3] to [5].
• A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion has 1 to 9 carbon atoms), and r is an integer of 1 to 5, preferably 1 to 3].
• Y is -R-O-, -R-CO-O-, or -R-O-CO-, where R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and n is an integer from 10 to 50.
• monofunctional phenols represented by the above formula [3] include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol, and isooctylphenol.
• the monofunctional phenols represented by the above formula [4] or [5] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and when they are used to block the ends of polycarbonate resin, they not only function as an end terminator or molecular weight regulator, but also improve the melt fluidity of the resin, facilitating molding and processing, and have the effect of lowering the water absorption rate of the resin, making them preferably used.
• substituted phenols of the above formula [4] those in which n is 10 to 30, particularly 10 to 26, are preferred, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol.
• a compound in which Y is -R-COO- and R is a single bond is suitable, and those in which n is 10 to 30, particularly 10 to 26, are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and tricontyl hydroxybenzoate.
• the monofunctional phenols represented by the above formula [3] are preferred, more preferably alkyl- or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p-cumylphenol, or 2-phenylphenol.
• These monofunctional phenol end terminators are desirably introduced into the terminals in an amount of at least 5 mol %, and preferably at least 10 mol %, of the total terminals of the resulting polycarbonate resin, and the end terminators may be used alone or in combination of two or more kinds.
• the polycarbonate resin used as component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof, within the scope of the present invention.
• aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof, within the scope of the present invention.
• the viscosity average molecular weight of the polycarbonate resin used as component A of the present invention is preferably in the range of 11,500 to 50,000, more preferably 12,500 to 40,000, even more preferably 13,500 to 35,000, and most preferably 15,000 to 30,000. If the molecular weight exceeds the upper limit, the melt viscosity may become too high and moldability may be poor, and if the molecular weight is below the lower limit, problems may occur in mechanical strength.
• the viscosity average molecular weight referred to in the present invention is first calculated by the specific viscosity calculated by the following formula using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20°C, and the specific viscosity thus calculated is inserted into the following formula to calculate the viscosity average molecular weight Mv.
• the polycarbonate resin used as component A of the present invention preferably has a total Cl (chlorine) content in the resin of 0 to 500 ppm, more preferably 0 to 350 ppm. If the total Cl content in the polycarbonate resin is in the above range, it is preferable because it has excellent hue and thermal stability.
• the triarylphosphine used as Component B in the present invention is a triarylphosphine having a specific structure represented by the following formula [1].
• Polycarbonate resin compositions and polycarbonate resin molded articles obtained by blending a triarylphosphine having this structure are inhibited from discoloring when exposed to a high-temperature environment.
• R 2-1 , R 2-2 , R 2-3 , R 6-1 , R 6-2 , R 6-3 , R 0-1 , R 0-2 and R 0-3 are hydrogen atoms, hydrocarbon groups, alkoxy groups or halogens and may be the same or different, provided that at least one of R 2-1 , R 2-2 , R 2-3 , R 6-1 , R 6-2 and R 6-3 is a hydrocarbon group, alkoxy group or halogen.
• p, q and r are each integers from 0 to 3.
• the hydrocarbon group is preferably an alkyl group, an aralkyl group, an alkenyl group or an aryl group.
• alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, etc.
• An alkyl group having 1 to 18 carbon atoms is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, an alkyl group having 1 to 8 carbon atoms is even more preferred, an alkyl group having 1 to 6 carbon atoms is particularly preferred, and an alkyl group having 1 to 4 carbon atoms is most preferred.
• aralkyl group examples include a benzyl group and a phenylethyl group.
• An aralkyl group having 7 to 20 carbon atoms is preferred, an aralkyl group having 7 to 15 carbon atoms is more preferred, and an aralkyl group having 7 to 10 carbon atoms is even more preferred.
• alkenyl group examples include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc.
• An alkenyl group having 2 to 10 carbon atoms is preferred, and an alkenyl group having 2 to 6 carbon atoms is more preferred.
• the aryl group examples include a phenyl group, a naphthyl group, etc.
• An aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.
• alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc.
• An alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred.
• the halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom.
• R 2-1 , R 2-2 , R 2-3 , R 6-1 , R 6-2 and R 6-3 is a hydrocarbon group, an alkoxy group or a halogen, and is preferably an alkyl group or an alkoxy group, particularly preferably an alkyl group having 1 to 4 carbon atoms.
• p, q and r each represent an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
• triarylphosphines of the above formula [1] include tri(o-tolyl)phosphine, tri(2,5-xylyl)phosphine, and tri(2,4-xylyl)phosphine.
• the content of triarylphosphine is preferably 0.001 to 0.1 parts by weight per 100 parts by weight of polycarbonate resin. 0.005 to 0.08 parts by weight is more preferable, and 0.01 to 0.07 parts by weight is even more preferable. If the content is less than the above range, the effect of inhibiting discoloration when exposed to a high-temperature environment may be reduced, and if the content exceeds the above range, triarylphosphine that volatilizes when heat is applied during molding processing may adhere to the mold, causing defects in the molded product.
• the polycarbonate resin composition of the present invention may contain known additives for imparting various functions to the molded article or improving the properties thereof, as long as the purpose of the present invention is not impaired. These additives will be described in detail below.
• Heat Stabilizers Various known heat stabilizers can be blended into the polycarbonate resin composition of the present invention. Specific examples include phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants.
• phosphorus-based antioxidants include phosphorous acid (phosphite), phosphonite, phosphinite, phosphine, phosphoric acid (phosphate), phosphonate, phosphinate, and phosphine oxide, of which phosphites, phosphonites, phosphines, phosphonates, and phosphates are preferably used.
• the phosphite compound include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenylpheny
• phosphite compounds those which react with dihydric phenols to have a cyclic structure can also be used.
• 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, etc. can be mentioned.
• Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-pheny
• Such phosphonite compounds can be used in combination with the phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred.
• phosphine compounds include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tris(p-tolyl)phosphine, tris(p-anisyl)phosphine, trinaphthylphosphine, and diphenylbenzylphosphine.
• a particularly preferred phosphine compound is triphenylphosphine.
• Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
• Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like, and preferably triphenyl phosphate and trimethyl phosphate.
• sulfur-based antioxidants include pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol tetrakis (3-stearyl thiopropionate), etc., and among these, pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate) dilauryl-3,3'-thiodipropionate, dimyristyl-3, Examples of such thiodipropionates include distearyl-3,3'-thiodipropionate, and of these, pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis
• phenolic antioxidants include vitamin E, n-octadecyl- ⁇ -(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis( 6- ⁇ -methyl-benzyl-
• the phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants listed above can each be used alone or in combination of two or more kinds.
• the content of these phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants is preferably 0.0001 to 1 part by weight per 100 parts by weight of component A. More preferably, it is 0.0005 to 0.5 parts by weight, and even more preferably, it is 0.001 to 0.2 parts by weight.
• a pentaerythritol diphosphite compound which is blended mainly for the purpose of suppressing discoloration at high temperatures when the polycarbonate resin composition of the present invention is processed into pellets using a melt kneader such as a vented twin-screw extruder, and suppressing discoloration when the polycarbonate resin composition of the present invention is processed into a desired molded product using an injection molding machine or the like.
• a triarylphosphine compound having a specific structure as component B in combination there is an effect of further improving transparency and light-guiding performance by suppressing yellowing during molding processing.
• dipentaerythritol diphosphite compounds that may be used include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, and bis(2,4-dicumylphenyl) pentaerythritol diphosphite.
• pentaerythritol diphosphite examples include phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.
• Preferred are bis(2,4-dicumylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and more preferred is bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
• the content of the pentaerythritol diphosphite compound is preferably 0.005 to 0.1 parts by weight, and more preferably 0.01 to 0.05 parts by weight, per 100 parts by weight of the polycarbonate resin of component A. If it is less than this range, the effect of inhibiting discoloration during molding and processing will be reduced, and transparency may deteriorate, while if it exceeds this range, the mechanical properties, dry heat resistance, and wet heat resistance of the material will decrease, and mold contamination during molding may occur.
• the polycarbonate resin composition of the present invention may contain a mold release agent as necessary.
• a mold release agent a known one may be used.
• saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (including polyethylene waxes or 1-alkene polymers. These may also be modified with a functional group-containing compound such as an acid modification), silicone compounds, fluorine compounds, paraffin wax, beeswax, and the like may be mentioned.
• saturated fatty acid esters, linear or cyclic polydimethylsiloxane oils, polymethylphenyl silicone oils, and fluorine oils are preferred.
• Particularly preferred mold release agents include saturated fatty acid esters, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin deca stearate and decaglycerin tetrastearate, lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacate behenate, and erythritol esters such as pentaerythritol tetrastearate are used.
• the content of such a mold releasing agent is preferably 0.01 to 1 part by weight per 100 parts by weight of the A component.
• the polycarbonate resin composition of the present invention may contain an ultraviolet absorber, if necessary.
• ultraviolet absorbers include benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, and bis(5-benzoyl-4-hydroxy-2-me
• ultraviolet absorbers examples include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis( ⁇ , ⁇ '- Benzotriazole-based ultraviolet absorbers such as dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetraphthalimidomethyl)-5'-methylphenyl]benzotri
• examples of the ultraviolet absorber include hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol and 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, and malonate compounds such as 2-(1-arylalkylidene)malonate esters such as Hostavin PR-25 manufactured by Clariant Japan and Hostavin B-CAP manufactured by Clariant Japan.
• the content of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, and more preferably 0.02 to 1 part by weight, per 100 parts by weight of the A component.
• the polycarbonate resin composition of the present invention may contain a light stabilizer as required.
• light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2n-butylmalonate, a condensate of 1,2,3,4-butanecarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and tridecyl alcohol, and a condensate of 1,2,3,4-butanedicarboxylic acid and 1,2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol.
• the polycarbonate resin composition of the present invention may contain a bluing agent to counteract the yellowish color due to an ultraviolet absorbing agent or the like. Any bluing agent that is normally used for polycarbonate resins may be used without any particular problems. In general, anthraquinone dyes are preferred because they are easily available. Specific examples of bluing agents include Solvent Violet 13 (CA. No. (Color Index No.) 60725; Trade Names: Bayer's "Macrolex Violet B", Mitsubishi Chemical's "Dia Resin Blue G", Sumitomo Chemical's "Sumiplast Violet B”); Solvent Violet 31 (CA. No. 68210; Trade Name: Mitsubishi Chemical's "Dia Resin Violet D”); Solvent Violet 33 (CA.
• the fluorescent brightening agent is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white, and examples thereof include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds.
• the fluorescent brightening agent has the effect of absorbing the ultraviolet energy of light and radiating this energy in the visible region.
• the content of the fluorescent brightening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the A component.
• the polycarbonate resin composition of the present invention may contain an epoxy compound as necessary.
• an epoxy compound is added for the purpose of improving the wet heat resistance of the polycarbonate resin composition, and can also suppress mold corrosion.
• all epoxy compounds having an epoxy functional group can be used.
• preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate.
• the amount of such an epoxy compound to be added is preferably 0.003 to 0.3 parts by weight, more preferably 0.004 to 0.2 parts by weight, even more preferably 0.005 to 0.15 parts by weight, and particularly preferably 0.01 to 0.1 parts by weight, relative to 100 parts by weight of component A.
• organic metal salt compound can be blended into the polycarbonate resin composition of the present invention.
• organic metal salts are blended for the purpose of imparting flame retardancy, and are preferably alkali (earth) metal salts of organic acids having 1 to 50, preferably 1 to 40 carbon atoms, and more preferably alkali (earth) metal salts of organic sulfonic acids.
• the alkali (earth) metal salts of organic sulfonic acids include metal salts of fluorine-substituted alkylsulfonic acids such as metal salts of perfluoroalkylsulfonic acids having 1 to 10, preferably 2 to 8 carbon atoms and alkali metals or alkaline earth metals, and metal salts of aromatic sulfonic acids having 7 to 50, preferably 7 to 40 carbon atoms and alkali metals or alkaline earth metals.
• alkali metals constituting the metal salts include lithium, sodium, potassium, rubidium, and cesium
• examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium.
• alkali metals are alkali metals.
• rubidium and cesium which have a larger ionic radius, are suitable when transparency is required, but they are not widely used and are difficult to purify, which may result in a disadvantage in terms of cost.
• metals with a smaller ionic radius such as lithium and sodium, may be disadvantageous in terms of flame retardancy.
• the alkali metals in the alkali metal sulfonates may be used differently, but in all respects, potassium sulfonates, which have an excellent balance of properties, are most suitable.
• Such potassium salts may also be used in combination with alkali metal sulfonates made of other alkali metals.
• alkali metal salts of perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfon
• the number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8. Of these, potassium perfluorobutanesulfonate is particularly preferred.
• fluoride ions are usually mixed in at least a small amount. The presence of such fluoride ions can be a factor in reducing flame retardancy, so it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography.
• the content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. It is also preferable that the content is 0.2 ppm or more for production efficiency.
• the alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ions can be produced by using a known production method, and by a method of reducing the amount of fluoride ions contained in the raw material when producing a fluorine-containing organic metal salt, a method of removing hydrogen fluoride obtained by the reaction by gas generated during the reaction or by heating, and a method of reducing the amount of fluoride ions by using a purification method such as recrystallization and reprecipitation during the production of a fluorine-containing organic metal salt.
• organic metal salt flame retardants are relatively soluble in water, it is preferable to manufacture them using ion-exchanged water, particularly water that has an electrical resistance of 18 M ⁇ cm or more, i.e., an electrical conductivity of approximately 0.55 ⁇ S/cm or less, and dissolving and washing the material at a temperature higher than room temperature, followed by cooling and recrystallization.
• aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butyl
• potassium salts are particularly preferred.
• potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are particularly preferred, and mixtures of these (with a weight ratio of the former to the latter of 15/85 to 30/70) are particularly preferred.
• alkali (earth) metal salts of sulfates and alkali (earth) metal salts of aromatic sulfonamides are suitable.
• alkali (earth) metal salts of sulfates alkali (earth) metal salts of sulfates of monohydric and/or polyhydric alcohols can be mentioned in particular.
• sulfates of monohydric and/or polyhydric alcohols methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfates of polyoxyethylene alkylphenyl ether, mono-, di-, tri-, and tetrasulfates of pentaerythritol, sulfates of lauric acid monoglyceride, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride can be mentioned.
• alkali (earth) metal salts of these sulfates alkali (earth) metal salts of lauryl sulfate are preferred.
• alkali (earth) metal salts of aromatic sulfonamides include saccharin, N-(p-tolylsulfonyl)-p-toluenesulfonimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and alkali (earth) metal salts of N-(phenylcarboxyl)sulfanilimide.
• the content of the organic metal salt is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, even more preferably 0.01 to 0.3 parts by weight, and particularly preferably 0.03 to 0.15 parts by weight, relative to 100 parts by weight of component A.
• the polycarbonate resin composition of the present invention can be blended with a polycaprolactone compound.
• a polycaprolactone compound has the effect of improving thermal stability when subjected to thermal history during molding or the like, and some of the hydrogen atoms of the methylene chain in the repeating unit of polycaprolactone (-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -C(O)-O-) may be substituted with a halogen atom or a hydrocarbon group.
• the terminal OH group of the polycaprolactone compound may be subjected to terminal treatment such as esterification or etherification, and the polycaprolactone compound may have a bifunctional, trifunctional or tetrafunctional structure such as polycaprolactone diol, polycaprolactone triol or polycaprolactone tetraol.
• the molecular weight of the polycaprolactone compound is in the range of 300 to 5,000 in terms of number average molecular weight in terms of polystyrene by GPC, and one in the range of 500 to 4,000 is preferably used.
• the amount of the polycaprolactone compound to be blended is preferably within the range of 0.2 to 1.5 parts by weight per 100 parts by weight of component A.
• polyalkylene glycol compound The polycarbonate resin composition of the present invention can be blended with a polyalkylene glycol compound.
• polyalkylene glycol compounds have the effect of improving thermal stability when subjected to thermal history during molding and the like, and specific examples thereof include polyalkylene glycols having 2 to 6 carbon atoms, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and derivatives thereof.
• the terminal OH group of the polyalkylene glycol may be subjected to terminal treatment such as esterification or etherification.
• the molecular weight of the polyalkylene glycol is in the range of 300 to 5,000 in terms of number average molecular weight in terms of polystyrene by GPC, and those in the range of 500 to 4,000 are preferably used.
• the blending amount of such polyalkylene glycol compounds is preferably in the range of 0.2 to 1.5 parts by weight relative to 100 parts by weight of component A.
• the resin composition of the present invention can be blended with known additives to impart various functions to molded products or improve their properties, as long as it does not impair the purpose of the present invention.
• known additives include reinforcing fillers, sliding agents (e.g. PTFE particles), colorants, fluorescent dyes, inorganic phosphors (e.g. phosphors with aluminate as the mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g. titanium oxide fine particles, zinc oxide fine particles), light diffusing agents, flow modifiers, radical generators, infrared absorbing agents (heat ray absorbing agents), and photochromic agents.
• sliding agents e.g. PTFE particles
• colorants e.g. PTFE particles
• fluorescent dyes e.g. phosphors with aluminate as the mother crystal
• antistatic agents e.g. phosphors with aluminate as the mother crystal
• any method can be used to produce the polycarbonate resin composition of the present invention.
• the A component, the B component, and any other components can be thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then granulated using an extrusion granulator or a briquetting machine, if necessary, and then melt-kneaded using a melt kneader, such as a vented twin-screw extruder, and pelletized using a pelletizer or other device.
• a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then granulated using an extrusion granulator or a briquetting machine, if necessary, and then melt-kneaded using a melt kneader, such as a vented twin-screw extruder, and pelletized
• the A component, the B component, and any other components can be independently supplied to a melt kneader, such as a vented twin-screw extruder, a method in which the A component and a part of the other components are premixed and then supplied to the melt kneader independently of the remaining components, a method in which the B component is diluted and mixed with water or an organic solvent and then supplied to the melt kneader, or a method in which such a diluted mixture is premixed with the other components and then supplied to the melt kneader.
• a so-called liquid injection device or liquid addition device can be used to supply the components to the melt kneader.
• any method can be used to produce a molded article made of the polycarbonate resin composition of the present invention.
• the polycarbonate resin composition can be kneaded in an extruder, a Banbury mixer, a roll, or the like, and then molded by a conventional method such as injection molding, extrusion molding, or compression molding.
• Molded articles made from the resin composition of the present invention can be suitably used in a variety of industrial applications, including in the fields of lighting, including LED lighting, office automation equipment, electrical and electronic equipment, automobiles, and building materials.
• the pellet-shaped polycarbonate resin composition obtained from each composition of the examples was dried in a hot air circulation dryer at 120 ° C. for 5 hours, and molded into a molded plate having a width of 50 mm, a length of 90 mm, and a thickness of 2 mm at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.]. This molded plate was heat-treated for 500 hours and 1000 hours in a hot air circulation dryer at 130 ° C.
• the yellowness index (YI) of the molded plate before and after the heat treatment was measured and calculated using an integrating sphere spectrophotometer [X-Rite CE-7000A (YI before and after 500 hours of heat treatment), X-Rite Ci7800 (YI before and after 1000 hours of heat treatment)] in accordance with ASTM-D1925 using a C light source, a viewing angle of 2 °, and a transmission method.
• the increase in YI ( ⁇ YI) of the molded plate after heat treatment was calculated from the following formula to evaluate the dry heat resistance. The larger the ⁇ YI, the more likely the polycarbonate resin is to turn yellow and the poorer the dry heat resistance.
• ⁇ YI YI after heat treatment - YI before heat treatment
• Examples A-1 to A-6 and Comparative Examples A-1 to A-6 The A component, B component, and other components were mixed in a blender in the amounts shown in Table 1, and then melt-kneaded using a vented twin-screw extruder to obtain a pellet-shaped polycarbonate resin composition.
• the vented twin-screw extruder used was TEX30 ⁇ (fully intermeshed, same-direction rotation, two-thread screw) manufactured by Japan Steel Works, Ltd.
• the extrusion conditions were a discharge rate of 30 kg/h, a screw rotation speed of 208 rpm, an extrusion temperature of 260°C, and a vent vacuum of 1 kPa.
• the obtained pellets were used to evaluate the dry heat resistance described in the evaluation method above. The evaluation results are shown in Table 1.
• A-1 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd., CM-1000, viscosity average molecular weight 15,000)
• A-2 Bisphenol A type aromatic polycarbonate resin prepared by blending 50 parts by weight of the above A-1 and 50 parts by weight of the following A-3, and adjusting the viscosity average molecular weight to 17,000.
• A-3 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd., L-1225WL, viscosity average molecular weight 18,500)
• A-4 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd.: L-1225WX, viscosity average molecular weight 20,000)
• B-1 Tri(o-tolyl)phosphine (Tokyo Chemical Industry Co., Ltd.)
• B-2 Tri(2,5-xylyl)phosphine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• C-1 Bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Revonox 608, manufactured by Chimei)
• C-2 Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (manufactured by ADEKA Corporation, PEP-36)
• E-1 Tri(o-tolyl)phosphin
• the pellet-shaped polycarbonate resin composition obtained from each composition of the Examples was dried in a hot air circulation dryer at 120°C for 5 hours, and molded into a molded product for light guide performance evaluation with a width of 10 mm, a thickness of 10 mm, and a length of 300 mm using an injection molding machine (Japan Steel Works, Ltd. J180ADS-110U) under the conditions of a molding temperature of 270°C, a mold temperature of 80°C, a molding cycle of 100 seconds, and a residence time of 220 seconds.
• the cavity and core parts of the mold used for this molding had a #5000 mirror finish, and the molded product was free of appearance defects such as silver, voids, sink marks, and flow marks, and evaluation was performed using a molded product with good appearance.
• a blue LED lamp (Opto Supply, ⁇ 5mm bullet-shaped LED, model: LP-V5YL5111A) was placed so that one end face of the molded product (face 10mm wide, 10mm thick) was 3mm away from the tip of the blue LED lamp.
• An illuminometer (digital illuminometer, model: LX-3000, manufactured by Custom) was installed so that the sensor tip of the illuminometer was 8 mm away from the end face of the molded product (face 10 mm wide and 10 mm thick) on the side opposite the face on which the blue LED lamp was placed.
• a 100V commercial power supply was transformed using a switching AC adapter (manufactured by GO FORWARD ENTERPRISE CORP., model: GF12-US0520) with an output of DC 5V, 2.0A, and the adapter was connected to a blue LED lamp and turned on.
• ⁇ White LED light guide performance evaluation> The same molded article for evaluating the light-guiding performance as that used in the evaluation of the light-guiding performance of the blue LED was used, and one end surface of this molded article (width 10 mm, thickness 10 mm) was measured in a dark room adjusted to a room temperature of 23°C.
• the white LED lamp was arranged so that the tip of the white LED lamp (manufactured by Nichia Kogyo, ⁇ 3 mm bullet-shaped LED, model: NSPW310DS, with an orifice ⁇ 2.2 mm attached to the tip) was 3 mm away from the surface of the white LED lamp.
• An illuminometer (digital illuminometer, model: LX-3000, manufactured by Custom) was installed so that the sensor tip of the illuminometer was 8 mm away from the end face of the molded product (face 10 mm wide and 10 mm thick) on the side opposite the face on which the white LED lamp was placed.
• a 100V commercial power supply was transformed using a switching AC adapter (manufactured by GO FORWARD ENTERPRISE CORP., model: GF12-US0520) with an output of DC 5V, 2.0A, and the adapter was connected to a white LED lamp and turned on.
• the pellet-shaped polycarbonate resin composition obtained from each composition of the Examples was dried in a hot air circulation dryer at 120°C for 5 hours, and molded into a molded plate having a width of 50 mm, a length of 90 mm and a thickness of 2 mm using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.] under conditions of a molding temperature of 270°C, a mold temperature of 80°C, a molding cycle of 50 seconds and a residence time of 100 seconds.
• the molded plate was heat-treated for 1000 hours in a hot air circulation dryer at 130 ° C.
• the yellowness index (YI) of the molded plate before heat treatment and the molded plate after heat treatment for 1000 hours was measured using an integrating sphere spectrophotometer (X-Rite Ci-7800) in accordance with ASTM-D1925, C light source, viewing angle 2 °, and transmission method.
• the increase in YI of the molded plate after heat treatment ( ⁇ YI) was calculated from the following formula, and the dry heat resistance was evaluated. The larger the ⁇ YI, the more likely the polycarbonate resin is to discolor to yellow, indicating poor dry heat resistance.
• ⁇ YI YI after 1000 hours of heat treatment - YI before heat treatment
• Examples B-1 to B-14, Comparative Examples B-1 to B-5 The A component, B component, C component, and other components were mixed in a blender in the amounts shown in Tables 2 and 3, and then melt-kneaded using a vented twin-screw extruder to obtain a pellet-shaped polycarbonate resin composition.
• the vented twin-screw extruder used was TEX30 ⁇ (fully interlocking, same-direction rotation, two-thread screw) manufactured by Japan Steel Works, Ltd.
• the extrusion conditions were a discharge rate of 30 kg/h, a screw rotation speed of 208 rpm, an extrusion temperature of 260°C, and a vent vacuum of 1 kPa.
• the obtained pellets were used to evaluate the blue LED light guide performance, white LED light guide performance, and dry heat resistance described in the evaluation method. The evaluation results are shown in Tables 2 and 3.
• blue LED light guiding performance of 75 lx (lux) or more is considered a pass
• white LED light guiding performance of 750 lx (lux) or more is considered a pass
• dry heat resistance of 1.0 or less is considered a pass.
• blue LED light guiding performance, white LED light guiding performance, and dry heat resistance must all be within the pass range to be considered a pass, with pass marks indicated as "O” and fail marks (outside the pass range) indicated as "X”.
• A-1 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd., CM-1000, viscosity average molecular weight 15,000)
• A-2 Bisphenol A type aromatic polycarbonate resin prepared by blending 50 parts by weight of the above A-1 and 50 parts by weight of the following A-3, and adjusting the viscosity average molecular weight to 17,000.
• A-3 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd., L-1225WL, viscosity average molecular weight 18,500)
• A-4 Bisphenol A type aromatic polycarbonate resin (Teijin Ltd.: L-1225WX, viscosity average molecular weight 20,000)
• B-1 Tri(o-tolyl)phosphine (Tokyo Chemical Industry Co., Ltd.)
• B-2 Tri(2,5-xylyl)phosphine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• C-1 Bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Revonox 608, manufactured by Chimei)
• C-2 Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (manufactured by ADEKA Corporation, PEP-36)
• D-1 Bis(2,4-dicumylpheny
• the pellet-shaped polycarbonate resin composition obtained from each composition of the Examples was dried in a hot air circulation dryer at 120°C for 5 hours, and molded into a molded product for light guide performance evaluation with a width of 10 mm, a thickness of 10 mm, and a length of 300 mm using an injection molding machine (Japan Steel Works, Ltd. J180ADS-110U) under the conditions of a molding temperature of 270°C, a mold temperature of 80°C, a molding cycle of 100 seconds, and a residence time of 220 seconds.
• the cavity and core parts of the mold used for this molding had a #5000 mirror finish, and the molded product was free of appearance defects such as silver, voids, sink marks, and flow marks, and evaluation was performed using a molded product with good appearance.
• a blue LED lamp (Opto Supply, ⁇ 5mm bullet-shaped LED, model: LP-V5YL5111A) was placed so that one end face of the molded product (face 10mm wide, 10mm thick) was 3mm away from the tip of the blue LED lamp.
• An illuminometer (digital illuminometer, model: LX-3000, manufactured by Custom) was installed so that the sensor tip of the illuminometer was 8 mm away from the end face of the molded product (face 10 mm wide and 10 mm thick) on the side opposite the face on which the blue LED lamp was placed.
• a 100V commercial power supply was transformed using a switching AC adapter (manufactured by GO FORWARD ENTERPRISE CORP., model: GF12-US0520) with an output of DC 5V, 2.0A, and the adapter was connected to a blue LED lamp and turned on.
• ⁇ White LED light guide performance evaluation> The same molded article for evaluating the light-guiding performance as that used in the evaluation of the light-guiding performance of the blue LED was used, and one end surface of this molded article (width 10 mm, thickness 10 mm) was measured in a dark room adjusted to a room temperature of 23°C.
• the white LED lamp was arranged so that the tip of the white LED lamp (manufactured by Nichia Kogyo, ⁇ 3 mm bullet-shaped LED, model: NSPW310DS, with an orifice ⁇ 2.2 mm attached to the tip) was 3 mm away from the surface of the white LED lamp.
• An illuminometer (digital illuminometer, model: LX-3000, manufactured by Custom) was installed so that the sensor tip of the illuminometer was 8 mm away from the end face of the molded product (face 10 mm wide and 10 mm thick) on the side opposite the face on which the white LED lamp was placed.
• a 100V commercial power supply was transformed using a switching AC adapter (manufactured by GO FORWARD ENTERPRISE CORP., model: GF12-US0520) with an output of DC 5V, 2.0A, and the adapter was connected to a white LED lamp and turned on.
• the pellet-shaped polycarbonate resin composition obtained from each composition of the Examples was dried in a hot air circulation dryer at 120°C for 5 hours, and molded into a molded plate having a width of 50 mm, a length of 90 mm and a thickness of 2 mm using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.] under conditions of a molding temperature of 270°C, a mold temperature of 80°C, a molding cycle of 50 seconds and a residence time of 100 seconds.
• the molded plate was heat-treated for 1000 hours in a hot air circulation dryer at 130 ° C.
• the yellowness index (YI) of the molded plate before heat treatment and the molded plate after heat treatment for 1000 hours was measured using an integrating sphere spectrophotometer [X-Rite Ci-7800] in accordance with ASTM-D1925, C light source, viewing angle 2 °, and transmission method.
• the increase in YI of the molded plate after heat treatment ( ⁇ YI) was calculated from the following formula, and the dry heat resistance was evaluated. The larger the ⁇ YI, the more likely the polycarbonate resin is to turn yellow and the poorer the dry heat resistance.
• ⁇ YI YI after 1000 hours of heat treatment - YI before heat treatment
• Examples C-1 to C-25, Comparative Examples C-1 to C-5 The A component, B component, C component, D component and other components were mixed in a blender in the respective blending amounts shown in Tables 4 to 6, and then melt-kneaded using a vented twin-screw extruder to obtain a pellet-shaped polycarbonate resin composition.
• the vented twin-screw extruder used was TEX30 ⁇ (fully intermeshed, same-direction rotation, two-thread screw) manufactured by Japan Steel Works, Ltd.
• the extrusion conditions were a discharge rate of 30 kg/h, a screw rotation speed of 208 rpm, an extrusion temperature of 260°C, and a vent vacuum of 1 kPa.
• the obtained pellets were used to evaluate the blue LED light guiding performance, white LED light guiding performance, dry heat resistance, and moist heat resistance described in the evaluation method. The evaluation results are shown in Tables 4 to 6.
• blue LED light guiding performance, white LED light guiding performance, dry heat resistance, and moist heat resistance must all be within the pass range to be pass, with pass marks indicated as "O” and fail marks (outside the pass range) indicated as "X”.
• the polycarbonate resin composition of the present invention exhibits excellent thermal stability with minimal discoloration in high-temperature environments, and molded articles obtained from the polycarbonate resin composition are extremely useful for a variety of industrial applications, including in the fields of LED lighting and other lighting, office automation equipment, electrical and electronic equipment, automobiles, and building materials.

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