WO2013147220A1 - ポリカーボネート樹脂の製造方法及びポリカーボネート樹脂組成物 - Google Patents

ポリカーボネート樹脂の製造方法及びポリカーボネート樹脂組成物 Download PDF

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WO2013147220A1
WO2013147220A1 PCT/JP2013/059663 JP2013059663W WO2013147220A1 WO 2013147220 A1 WO2013147220 A1 WO 2013147220A1 JP 2013059663 W JP2013059663 W JP 2013059663W WO 2013147220 A1 WO2013147220 A1 WO 2013147220A1
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Prior art keywords
polycarbonate resin
group
compound
resin composition
ppm
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English (en)
French (fr)
Japanese (ja)
Inventor
浩喜 柴田
涼平 西原
山本　正規
勝久 熊澤
成俊 兵頭
鶴原　謙二
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to IN7877DEN2014 priority Critical patent/IN2014DN07877A/en
Priority to CN201380017045.3A priority patent/CN104204033B/zh
Priority to KR1020147026674A priority patent/KR101959599B1/ko
Publication of WO2013147220A1 publication Critical patent/WO2013147220A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

  • the present invention relates to a method for producing a polycarbonate resin and a polycarbonate resin composition containing the obtained polycarbonate resin.
  • the present invention relates to a polycarbonate resin composition having a good color tone and a method for producing the same.
  • Polycarbonate resins are extremely high in transparency, heat resistance, mechanical strength, impact resistance, etc., have many excellent properties, and are used in large quantities in a wide range of fields. Specific examples include various machine parts, various electrical insulating materials, automobile parts, information equipment materials such as optical disks, and safety protection materials such as helmets.
  • a melting method in which a dihydroxy compound and a carbonic acid diester are subjected to a polycondensation reaction, an interface method in which the dihydroxy compound and carbonyl chloride are reacted at a phase interface between a solvent and an alkaline aqueous solution, and the like are known. Yes.
  • a transesterification catalyst is used as a polycondensation catalyst.
  • alkaline aqueous solutions see Patent Document 1
  • triarylphosphine see Patent Document 2
  • catalysts are known as catalysts.
  • a method of adding and adding other components is known.
  • a composition containing a specific phosphine and an aliphatic carboxylic acid ester is disclosed as a polycarbonate resin composition having good optical properties and good hydrolyzability as well as melt fluidity (Patent Document 3). reference).
  • Non-Patent Document 1 a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzoxazine ultraviolet absorber, or the like to a polycarbonate resin is widely known (for example, Non-Patent Document 1). reference).
  • Patent Document 4 discloses a polycarbonate resin composition in which a specific amount of a flame retardant is blended with a polycarbonate resin obtained by a melting method.
  • Japanese Unexamined Patent Publication No. 2005-146050 Japanese Unexamined Patent Publication No. 2009-108139 Japanese Unexamined Patent Publication No. 2011-80059 Japanese Unexamined Patent Publication No. 2003-090661
  • the present invention suppresses deterioration of hue, transparency and mechanical strength when used in a place exposed to ultraviolet rays or visible light for a long time, has a good color tone, and has improved flame retardancy and heat and humidity resistance. It is an object of the present invention to provide a polycarbonate resin, a composition containing the polycarbonate resin, and a method for producing the composition.
  • the present invention has the following gist.
  • a method for producing a polycarbonate resin in which a carbonic acid diester and a dihydroxy compound are subjected to a polycondensation reaction in the presence of a transesterification catalyst A phosphorus compound in which the transesterification catalyst is represented by the following general formula (1) and / or (2); Selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen), long-period periodic table group 2 elements, basic boron compounds, basic phosphorus compounds, and nitrogen-containing basic compounds.
  • a process for producing a polycarbonate resin comprising: (In Formula (1), Ph 1 , Ph 2 , and Ph 3 each independently represents an aromatic ring which may have a substituent.
  • substituent include an alkyl group having 1 to 30 carbon atoms, Represents an alkoxy group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, or an aromatic ring, and in formula (2), R 7 , R 8 , and R 9 each independently represents 4 to 30 represents an alkyl group or a cycloalkyl group, and when one or two of R 7 , R 8 , and R 9 are an alkyl group or a cycloalkyl group having 4 to 30 carbon atoms, the remaining two Or one may be the same as Ph 1 above.)
  • the above basic compound is at least one selected from the group consisting of a compound of a long-period periodic table group 1 element (excluding hydrogen) and a long-period periodic table group 2 element compound
  • R 1 to R 6 each independently represents a hydrogen atom or a methyl group.
  • [7] The phosphorus compound represented by the above (1) and / or (2) in the polycarbonate resin according to [6], Selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen), long-period periodic table group 2 elements, basic boron compounds, basic phosphorus compounds, and nitrogen-containing basic compounds. At least one basic compound and an ultraviolet absorber; A polycarbonate resin composition comprising.
  • [8] The phosphorus compound represented by (1) and / or (2) above in the polycarbonate resin according to [6], Selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen), long-period periodic table group 2 elements, basic boron compounds, basic phosphorus compounds, and nitrogen-containing basic compounds.
  • a polycarbonate resin composition comprising.
  • the above-mentioned basic compound is at least one selected from the group consisting of a compound of a long-period periodic table group 1 element (excluding hydrogen) and a long-period periodic table group 2 element compound.
  • the polycarbonate resin composition according to [7] or [8].
  • the above [7] to [9], wherein the content of the phosphorus compound represented by the general formula (1) and / or (2) is 1 ppm or more and 100 ppm or less with respect to the entire polycarbonate resin composition.
  • the polycarbonate resin composition in any one.
  • the phosphorus compound represented by the general formula (1) is composed of triphenylphosphine, tris (p-methylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, and tris (p-tertiarybutylphenyl) phosphine.
  • the polycarbonate resin composition according to any one of [14].
  • the flame retardant is at least one selected from the group consisting of metal sulfonate flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants.
  • the polycarbonate resin composition in any one of [13] and [16].
  • the present invention by using a specific phosphorus compound and a specific basic compound as a transesterification catalyst, side reactions can be suppressed, and the color tone of the obtained polycarbonate resin can be improved.
  • a polycarbonate resin having excellent properties can be obtained.
  • the polycarbonate resin composition containing the polycarbonate resin of the present invention suppresses deterioration of hue, transparency, and mechanical strength even when used in a place exposed to ultraviolet rays or visible light for a long time, and is difficult. Improved flame resistance and heat and humidity resistance.
  • a polycarbonate resin is produced by polycondensation reaction in the presence of a transesterification catalyst using a carbonic acid diester and a dihydroxy compound as raw materials.
  • a transesterification catalyst using a carbonic acid diester and a dihydroxy compound as raw materials.
  • Carbonated diester examples of the carbonic acid diester that is one raw material of the polycarbonate resin include diphenyl carbonate (hereinafter sometimes referred to as “DPC”), substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-. Examples thereof include dialkyl carbonates such as butyl carbonate. These carbonic acid diesters can be used alone or in admixture of two or more.
  • DPC diphenyl carbonate
  • substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-.
  • dialkyl carbonates such as butyl carbonate.
  • the carbonic acid diester may preferably be substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of 50 mol% or less, more preferably 30 mol% or less.
  • Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.
  • Carbonic acid diester (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) is used in excess relative to the dihydroxy compound. That is, the carbonic acid diester is used in an amount of 1.01 to 1.30 times (molar ratio), preferably 1.02 to 1.20 times (molar ratio) with respect to the dihydroxy compound.
  • the molar ratio is too small, the terminal hydroxyl groups of the obtained polycarbonate resin increase, and the thermal stability of the polycarbonate resin tends to deteriorate.
  • the transesterification reaction rate decreases, making it difficult to produce a polycarbonate resin having a desired molecular weight, or increasing the residual amount of carbonic acid diester in the polycarbonate resin. May cause odor when molded. Further, the terminal hydroxyl group of the obtained polycarbonate resin is reduced, and when the polycarbonate resin is used in a place where it is exposed to ultraviolet rays or visible light for a long time, deterioration of hue, transparency, and mechanical strength may be insufficiently suppressed. .
  • the dihydroxy compound which is the other raw material of the polycarbonate resin is a compound having two hydroxyl groups in the molecule.
  • the dihydroxy compound has one or more aromatic rings in the molecule, It is preferable to use an aromatic dihydroxy compound in which each hydroxyl group is bonded to an aromatic ring.
  • aromatic dihydroxy compound examples include, for example, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl) propane.
  • 2,2-bis (4-hydroxy-3-t-butylphenyl) propane 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like bisphenols; 4,4′-dihydroxybiphenyl, 3,3 ′ , 5,5′-tetramethyl-4,4′-dihydroxybiphenyl and the like; bis (4-hydroxyphenyl) sulfur Hong, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
  • Transesterification catalyst examples include a catalyst that uses a combination of a phosphorus compound and a basic compound.
  • a phosphorus compound the phosphorus compound represented by the following general formula (1) or (2) is mentioned.
  • Ph 1 , Ph 2 , and Ph 3 each independently represent an aromatic ring that may have a substituent.
  • substituents include an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, and an aromatic ring.
  • phosphorus compound represented by the general formula (1) examples include compounds represented by the following formulas (8) to (12 ′).
  • Ph 1 , Ph 2 , and Ph 3 satisfy the above-described requirements, and the dimer has two phosphorus atoms via a substituent. It may be a compound. Examples of such a compound include compounds represented by the following formulas (13) to (16). As the phosphorus compound represented by the general formula (1), the formulas (8), (9) and (13) are particularly preferable.
  • R 7 , R 8 , and R 9 each independently represents an alkyl group or a cycloalkyl group having 4 to 30 carbon atoms.
  • R 7 , R 8 , and R 9 are an alkyl group or a cycloalkyl group having 4 to 30 carbon atoms, the rest may be the above Ph 1 .
  • Examples of the phosphorus compound represented by the general formula (2) include compounds represented by the following formulas (17) to (21).
  • R 7 , R 8 , and R 9 may satisfy the above requirements and may be a dimeric compound having two phosphorus atoms through a substituent.
  • Examples of such a compound include compounds represented by the following formulas (22) to (23).
  • the compound represented by the general formula (2) is particularly preferably tributylphosphine.
  • the phosphorus compounds represented by the general formula (1) or (2) can be used alone or in admixture of two or more.
  • preferable phosphorus compounds in the transesterification catalyst include triphenylphosphine, tris (p-methylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, and tris (p-tertiarybutylphenyl) phosphine. .
  • a compound of a long-period periodic table group 1 element (excluding hydrogen) (hereinafter sometimes referred to as “group 1 element (excluding hydrogen)”), a long period
  • group 1 element (excluding hydrogen) a compound of a long-period periodic table group 1 element (excluding hydrogen)
  • group 1 element excluding hydrogen
  • examples include at least one basic compound selected from the group consisting of compounds of Group 2 elements of the periodic table, basic boron compounds, basic phosphorus compounds, and nitrogen-containing basic compounds.
  • at least one selected from the group consisting of compounds of Group 1 elements (excluding hydrogen) and compounds of Group 2 elements is preferable.
  • Group 1 elements (excluding hydrogen) include group 1 elements (excluding hydrogen), inorganic compounds such as hydroxides, carbonates, hydrogen carbonate compounds; Group 1 elements (excluding hydrogen) , Organic compounds such as salts with phenols and organic carboxylic acids.
  • examples of the Group 1 element (excluding hydrogen) include lithium, sodium, potassium, rubidium, and cesium.
  • cesium compounds are preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.
  • Examples of Group 2 element compounds include hydroxides such as beryllium, magnesium, calcium, strontium, and barium, inorganic compounds such as carbonates; salts with these alcohols, phenols, and organic carboxylic acids. It is done. Of these Group 2 element compounds, magnesium compounds are preferred.
  • Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, and strontium salts of boron compounds.
  • the boron compound for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl Examples include benzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.
  • Examples of the basic phosphorus compound include trivalent phosphorus compounds such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, and tributylphosphine, or derivatives thereof. And quaternary phosphonium salts.
  • Examples of the nitrogen-containing basic compound include basic ammonium compounds and amine compounds.
  • Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltol Phenyl ammonium hydroxide, butyltriphenyl ammonium hydroxide, and
  • amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
  • the use ratio of the phosphorus compound and the basic compound represented by the above formula (1) and / or (2) is preferably from 10000: 1 to 0.1: 1 in phosphorus compound: basic compound (molar ratio), 5000: 1 to 1: 1 is more preferable. More preferably, it is 2000: 1 to 2: 1, most preferably 1000: 1 to 10: 1. When deviating from the above range, there may be a problem that the amount of by-products increases.
  • the amount of the phosphorus compound used is preferably 0.1 ⁇ mol or more, more preferably 1 ⁇ mol or more, still more preferably 10 ⁇ mol or more with respect to 1 mol of the dihydroxy compound.
  • the amount is less than 0.1 ⁇ mol, the polymerization activity decreases, and in order to obtain a predetermined molecular weight, the residence time must be lengthened, and the color tone may deteriorate.
  • the upper limit of the amount of the phosphorus compound used is preferably 1000 ⁇ mol, more preferably 500 ⁇ mol. When the amount is more than 1000 ⁇ mol, there may be a problem that by-products increase.
  • the transesterification catalyst may be used in advance as an aqueous solution.
  • concentration of the catalyst aqueous solution is not particularly limited, and is adjusted to an arbitrary concentration according to the solubility of the catalyst in water. Moreover, it can replace with water and can select other solvents, such as phenol, acetone, alcohol, and toluene.
  • the property of water used for dissolving the transesterification catalyst is not particularly limited as long as the kind and concentration of impurities contained are constant, but usually distilled water, deionized water, and the like are preferably used.
  • the polycarbonate resin is produced by mixing a raw material dihydroxy compound and a carbonic acid diester compound and reacting the raw material mixture in a molten state in the polycondensation reaction apparatus in the presence of the transesterification catalyst (melt polycondensation method). ).
  • a batch system, a continuous system, a combination thereof, or the like can be used for this reaction step.
  • the reaction is stopped, and then the step of removing devolatilized unreacted raw materials and reaction by-products in the polymerization reaction liquid, the step of adding a thermal stabilizer, a release agent, etc.
  • a polycarbonate resin is manufactured through a process of forming pellets having a particle size of 1 mm.
  • the step of the polycondensation reaction is usually performed continuously in a multistage system of two or more stages, preferably 3 to 7 stages.
  • Specific reaction conditions are temperature: 150 to 320 ° C., pressure: normal pressure to 0.01 Torr (1.3 Pa), average residence time: 5 to 150 minutes, preferably 5 to 300 minutes, preferably Temperature: 180 to 310 ° C., pressure: 20 to 0.05 Torr (2.7 kPa to 6.7 Pa), average residence time: 60 to 150 minutes.
  • the reaction temperature is increased stepwise. Set to a higher vacuum.
  • a plurality of reactors including a vertical reactor are provided to advance the polycondensation reaction as much as possible to increase the viscosity average molecular weight of the polycarbonate resin.
  • 3 to 6 groups, preferably 4 to 5 groups are installed.
  • FIG. 1 shows three vertical reactors 11a to 11c and one horizontal reactor 11d.
  • the melt of the raw material mixture A is supplied to the first vertical reactor 11a, and the polycondensation reaction is started in the presence of the transesterification catalyst.
  • the melt is sequentially sent to the vertical reactor 11b, the vertical reactor 11c, and the horizontal reactor 11d to advance the polycondensation reaction.
  • phenol is produced as a by-product, which is liquefied by a heat exchanger and sent to the phenol tank 13.
  • the phenol in the phenol tank 13 is appropriately treated and reused as a raw material for a dihydroxy compound or a carbonic acid diester compound.
  • a horizontal reactor 11d is used as the last reactor in the series of polycondensation reaction apparatus groups. This is because, as the polycondensation reaction proceeds, the viscosity of the melt increases, and in the last reactor, the viscosity becomes high, but stirring is easier.
  • the polycarbonate resin obtained in the polycondensation reaction step is cooled after devolatilization.
  • vertical and horizontal reactors for example, stirred tank reactors, thin film reactors, centrifugal thin film evaporation reactors, surface renewal biaxial kneading reactors, biaxial horizontal stirring reactors, wet wall reactors
  • a perforated plate reactor that polymerizes while being dropped freely, a perforated plate reactor that is polymerized while being dropped along a wire, and the like are used.
  • a stirring tank type reactor and a biaxial horizontal type stirring reactor are preferable.
  • Examples of the type of agitator blades in the vertical reactor include turbine blades, paddle blades, fiddler blades, anchor blades, full zone blades (manufactured by Shinko Pantech Co., Ltd.), Sunmeler blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max Blend blades (Sumitomo) Heavy machinery industry), helical ribbon blades, twisted lattice blades (manufactured by Hitachi, Ltd.), and the like.
  • a stirring blade a Max blend blade (made by Sumitomo Heavy Industries, Ltd.) and a helical ribbon blade are preferable.
  • the horizontal reactor means that the rotating shaft of the stirring blade is horizontal (horizontal direction).
  • a stirring blade of a horizontal reactor for example, a uniaxial stirring blade such as a disk type or a paddle type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries), Vivolac (manufactured by Sumitomo Heavy Industries, Ltd.), glasses
  • biaxial stirring blades such as blades and lattice blades (manufactured by Hitachi, Ltd.).
  • biaxial stirring blades such as a spectacle blade and a lattice blade (manufactured by Hitachi, Ltd.) are preferably used.
  • R 1 to R 6 each independently represent a hydrogen atom or a methyl group.
  • the total content of these by-products is preferably 750 ppm or less, more preferably 500 ppm or less, based on the entire polycarbonate resin. If it exceeds 750 ppm, the color tone may be deteriorated. On the other hand, the lower limit of the total amount is preferably 0 ppm, but it is practically difficult, and from the viewpoint of product color tone, about 100 ppm is acceptable.
  • the viscosity average molecular weight of the polycarbonate resin of the present invention is preferably 25,000 or less, more preferably 24,000 or less, and further preferably 23,000 or less. Further, the viscosity average molecular weight is preferably 15,000 or more, and more preferably 18,000 or more. When the viscosity average molecular weight is larger than 25,000, the viscosity becomes too high, which may cause molding failure. Further, when the viscosity average molecular weight is less than 15,000, the mechanical strength may be lowered. Further, the terminal hydroxyl group concentration of the polycarbonate resin is preferably 15000 ppm or less, more preferably 1200 ppm or less, further preferably 800 ppm or less, and most preferably 600 ppm or less.
  • 200 ppm or more is preferable and 300 ppm or more is more preferable. Even if the amount of terminal hydroxyl groups is too much or too little, there is a risk that deterioration in hue, transparency, and mechanical strength will be insufficient when used in a place exposed to ultraviolet rays or visible light for a long time.
  • the polycarbonate resin composition of the present invention includes a phosphorus compound represented by the following general formula (1) and / or a phosphorus compound represented by the following general formula (2) and a long-period periodic table first in the above polycarbonate resin.
  • At least one basic compound selected from the group consisting of compounds of group elements (excluding hydrogen), compounds of group 2 elements, basic boron compounds, basic phosphorus compounds and nitrogen-containing basic compounds, and UV absorbers And / or a flame retardant.
  • Ph 1 , Ph 2 , and Ph 3 each independently represents an aromatic ring which may have a substituent.
  • the substituent is an alkyl group having 1 to 30 carbon atoms, carbon An alkoxy group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, or an aromatic ring.
  • R 7 , R 8 , and R 9 each independently represents an alkyl group or cycloalkyl group having 4 to 30 carbon atoms.
  • the rest when one or two of Ph 1 , Ph 2 , and Ph 3 are aromatic rings that may have a substituent, the rest may be the same as R 7 described above.
  • R 7 , R 8 , and R 9 are an alkyl group or a cycloalkyl group having 4 to 30 carbon atoms, the rest may be the same as Ph 1 above.
  • polycarbonate resin examples include various polycarbonate resins obtained by a melt method in which a dihydroxy compound and a carbonic acid diester are polycondensed or an interface method in which a dihydroxy compound and carbonyl chloride are reacted at a phase interface between a solvent and an aqueous alkali solution. Can be used.
  • the present invention is suitably applied to the polycarbonate resin obtained by polycondensation of the former carbonic diester and dihydroxy compound in the presence of a transesterification catalyst.
  • the dihydroxy compound that is the raw material of the polycarbonate resin is a compound having two hydroxyl groups in the molecule.
  • the compound has one or more aromatic rings in the molecule, and two hydroxyl groups. It is preferable to use an aromatic dihydroxy compound in which each is bonded to an aromatic ring. Specific examples of such aromatic dihydroxy compounds are as described above for (dihydroxy compounds), and can be used alone or in admixture of two or more.
  • Examples of the carbonic acid diester that is the other raw material of the polycarbonate resin include diphenyl carbonate (hereinafter sometimes referred to as “DPC”), substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di- Examples thereof include dialkyl carbonates such as t-butyl carbonate. These carbonic acid diesters can be used alone or in admixture of two or more.
  • DPC diphenyl carbonate
  • substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di- Examples thereof include dialkyl carbonates such as t-butyl carbonate.
  • phosphorus compound represented by general formula (1) and / or (2) As a phosphorus compound, the compound represented by the following formula
  • Ph 1 , Ph 2 , and Ph 3 may be a dimeric compound that satisfies the above requirements and has two phosphorus atoms via a substituent.
  • Examples of such compounds include compounds represented by the above formulas (13) to (16).
  • Ph represents any one of Ph 1 , Ph 2 , and Ph 3 satisfying the above requirements.
  • the compound represented by the general formula (1) is composed of triphenylphosphine, tris (p-methylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, and tris (p-tertiarybutylphenyl) phosphine. It is preferably at least one compound selected from the group.
  • R 7 , R 8 and R 9 are all the same as defined above.
  • R 7 , R 8 , and R 9 are an alkyl group or a cycloalkyl group having 4 to 30 carbon atoms
  • the rest may be the same as Ph 1 and / or Ph 2 above.
  • a combination of R 7 , R 8 , Ph 1 or a combination of R 7 , Ph 1 , Ph 2 may be used.
  • Examples of the phosphorus compound represented by the general formula (2) include tributylphosphine, trihexylphosphine, trioctylphosphine, compounds represented by the above formulas (17) to (21), and the like.
  • R 7 , R 8 , and R 9 may be a dimer compound that satisfies the above requirements and has two phosphorus atoms via a substituent.
  • Examples of such compounds include compounds represented by the above formulas (22) to (23).
  • the compound represented by the general formula (2) is tributylphosphine.
  • the content of the compound represented by the general formula (1) and / or the phosphorus compound represented by the general formula (2) in the polycarbonate resin composition of the present invention is 1 ppm (weight ppm) with respect to the polycarbonate resin composition. The same shall apply hereinafter)) to 100 ppm or less, preferably 10 ppm to 80 ppm, more preferably 20 ppm to 60 ppm.
  • the content of the phosphorus compound is less than 1 ppm, the deterioration of hue, transparency, and mechanical strength may be insufficient when used in a place exposed to ultraviolet rays or visible light for a long time. If it exceeds 100 ppm, there is a risk of bleeding out during molding, resulting in poor appearance or a large amount of decomposition gas.
  • the basic compound is at least one member selected from the group consisting of compounds of Group 1 elements (excluding hydrogen), compounds of Group 2 elements, basic boron compounds, basic phosphorus compounds, and nitrogen-containing basic compounds. It is a basic compound and is preferably at least one compound selected from the group consisting of compounds of Group 1 elements (excluding hydrogen) and compounds of Group 2 elements.
  • Group 1 elements (excluding hydrogen) include group 1 elements (excluding hydrogen), inorganic compounds such as hydroxides, carbonates and hydrogen carbonate compounds; Group 1 elements (excluding hydrogen) alcohols. , Organic compounds such as salts with phenols and organic carboxylic acids.
  • the compound of the Group 1 element (excluding hydrogen) is at least one selected from the group consisting of a carbonate of the Group 1 element (excluding hydrogen) and an acetate of the Group 1 element (excluding hydrogen). A compound is preferred.
  • Group 1 elements include lithium, sodium, potassium, rubidium, and cesium. Of these compounds having a metal element, a cesium compound is preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.
  • examples of the Group 2 element include beryllium, magnesium, calcium, strontium, barium, and the like.
  • examples of compounds having these metal elements include hydroxides such as beryllium, magnesium, calcium, strontium, and barium, inorganic compounds such as carbonates; salts with these alcohols, phenols, and organic carboxylic acids.
  • the compound having the metal element is preferably at least one compound selected from the group consisting of carbonates of the metal elements and acetates of the metal elements.
  • the content of at least one selected from the group consisting of compounds of Group 1 elements (excluding hydrogen) and Group 2 elements is 0.01 ppm or more and 1 ppm or less with respect to the polycarbonate resin composition, Preferably they are 0.05 ppm or more and 1 ppm or less, More preferably, they are 0.1 ppm or more and 0.5 ppm or less. If the content of the compound is less than 0.01 ppm, the hue may be deteriorated. If it exceeds 1 ppm, there is a risk that suppression of deterioration of hue, transparency, and mechanical strength is insufficient when used in a place exposed to ultraviolet rays or visible light for a long time.
  • the ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability, and examples thereof include organic compounds and inorganic compounds having ultraviolet absorbing ability. Of these, organic compounds are preferred because they are easy to ensure affinity with the polycarbonate resin and are easily dispersed uniformly.
  • the molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Moreover, it is 600 or less normally, Preferably it is 450 or less, More preferably, it is 400 or less. If the molecular weight is too small, there is a possibility of causing a decrease in UV resistance performance after long-term use. When the molecular weight is excessively large, there is a possibility that the transparency of the resin composition is lowered after long-term use.
  • Preferred ultraviolet absorbers include benzotriazole compounds, hydroxybenzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, and the like. It is done. Of these, benzotriazole compounds, triazine compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferably used. These may be used alone or in combination of two or more.
  • benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, (2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazol Methyl -3- (3- (2H- benzotriazol-2
  • hydroxybenzophenone compounds examples include 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like.
  • malonic ester compounds examples include 2- (1-arylalkylidene) malonic esters, tetraethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, and the like.
  • triazine compounds examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, 2- (4,6-diphenyl-1,3, And 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy, Tinuvin 1577FF).
  • Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
  • Examples of the oxalic acid anilide compound include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor VSU).
  • ultraviolet absorbers examples include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole and 2- (2′-hydroxy-3′-tert-butyl-5′-hexylphenyl) benzo Triazole, (2- (2′-hydroxy-5′-tert-octylphenyl) -2H-benzotriazole, etc. are preferably used.
  • the content of the ultraviolet absorber is 0.01 ppm or more and 10000 ppm or less, preferably 0.01 ppm or more and 5000 ppm or less, more preferably 0.01 ppm or more and 3000 ppm or less with respect to the polycarbonate resin composition. If the content of the ultraviolet absorber is too small, there is a possibility that the effect of improving the color tone cannot be exhibited. If the amount is too large, bleeding may occur during molding, resulting in poor appearance or a large amount of decomposition gas.
  • the polycarbonate resin composition of the present invention is a polycarbonate resin composition to which a flame retardant is added
  • the polycarbonate resin composition exhibits a further remarkable flame retardant effect.
  • the flame retardant to be used include at least one selected from the group consisting of sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, a sulfonic acid metal salt flame retardant is preferable.
  • Examples of the sulfonic acid metal salt flame retardant include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts.
  • Examples of the metal of these metal salts include long-period periodic table group 1 metals such as sodium, lithium, potassium, rubidium, and cesium; magnesiums such as beryllium and magnesium; and long-period periodic tables such as calcium, strontium, and barium. Examples include Group 2 metals.
  • the sulfonic acid metal salt flame retardant can be used alone or in combination of two or more.
  • Examples of the sulfonic acid metal salts include aromatic sulfonesulfonic acid metal salts and perfluoroalkane-sulfonic acid metal salts.
  • the blending amount of the flame retardant used in the present invention is usually 0.001 ppm or more, preferably 0.002 ppm or more, based on the polycarbonate resin composition. If the blending amount of the flame retardant is excessively small, the flame retardant effect is lowered. If the blending amount of the flame retardant is excessively large, the heat and humidity resistance is lowered and the color tone may be deteriorated. Therefore, the blending amount of the flame retardant is usually preferably 0.001 ppm or more and 25% by weight or less with respect to the entire polycarbonate resin composition. In addition, the compounding quantity of a flame retardant changes greatly with the kind of flame retardant to be used.
  • the sulfonic acid metal salt flame retardant is preferably 0.001 ppm (weight ppm, the same shall apply hereinafter) to 0.1% by weight, more preferably 0.002 ppm to 0.05% by weight, based on the polycarbonate resin composition. More preferably, 0.004 ppm to 0.01% by weight is added.
  • aromatic sulfonesulfonic acid metal salt examples include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4,4′-dibromodiphenyl-sulfone-3-sulfonate, 4 , 4'-dibromodiphenyl-sulfone-3-sulfonic acid potassium, 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid calcium, diphenylsulfone-3,3'-disulfonic acid disodium, diphenylsulfone-3,3 Examples include dipotassium di-sulfonate.
  • perfluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.
  • halogen-containing compound flame retardant examples include, for example, tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromo
  • examples include allyl ether, tetrabromobisphenol A carbonate oligomer, ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane and the like.
  • the halogen-containing compound flame retardant is preferably added in an amount of 5 to 25% by weight, more preferably 10 to 22% by weight, based on the polycarbonate resin composition.
  • Examples of the phosphorus-containing compound flame retardant include red phosphorus, coated red phosphorus, polyphosphate compound, phosphate ester compound, and phosphazene compound.
  • phosphate ester compound examples include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl.
  • Phosphate diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3- Dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A bisphosphate, hydro Non bisphosphate, resorcinol bisphosphate, trioxybenzene phosphate.
  • the phosphorus-containing compound-based flame retardant is preferably added in an amount of 3 to 25% by weight, more preferably 5 to 15% by weight, and most preferably 10 to 12% by weight, based on the polycarbonate resin composition.
  • Examples of the silicon-containing compound-based flame retardant include silicone varnish, silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain having a branched structure. And a silicone compound having an aromatic group in the organic functional group contained therein, a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of silica powder, and an organopolysiloxane-polycarbonate copolymer Examples include coalescence.
  • the silicon-containing compound flame retardant is preferably added in an amount of 3 to 25% by weight, more preferably 5 to 15% by weight, and most preferably 10 to 12% by weight, based on the polycarbonate resin composition.
  • the polycarbonate resin composition of the present invention When the polycarbonate resin composition of the present invention is hydrolyzed, compounds as shown in the above general formulas (3) to (7) are produced, and these by-products are contained in the resin composition.
  • the content of these compounds can be measured by analyzing the polycarbonate resin after hydrolysis.
  • the total content of these compounds is preferably 750 ppm or less, more preferably 500 ppm or less, based on the entire polycarbonate resin.
  • the lower limit of the total amount is preferably 0 ppm, but it is practically difficult, so it may be about 100 ppm from the viewpoint of product color tone.
  • the viscosity average molecular weight of the polycarbonate resin contained in the polycarbonate resin composition of the present invention is preferably 25,000 or less, and more preferably 24,000 or less. Further, the viscosity average molecular weight is preferably 15,000 or more, and more preferably 18,000 or more. If the viscosity average molecular weight is greater than 25,000, the viscosity may be too high, resulting in poor molding. Further, if the viscosity average molecular weight is less than 15,000, the mechanical strength may be lowered.
  • the terminal hydroxyl group concentration of the polycarbonate resin contained in the polycarbonate resin composition of the present invention is preferably 1200 ppm or less, more preferably 800 ppm or less, and most preferably 600 ppm or less. Moreover, 200 ppm or more is preferable and 300 ppm or more is more preferable. Even if the amount of terminal hydroxyl groups is too much or too little, there is a risk that deterioration in hue, transparency, and mechanical strength will be insufficient when used in a place exposed to ultraviolet rays or visible light for a long time.
  • the polycarbonate resin composition of the present invention is a compound of the above polycarbonate resin (a compound represented by the general formula (1) and / or a phosphorus compound represented by the general formula (2) and a group 1 element (excluding hydrogen). , A group 2 element compound, a basic boron compound, a basic phosphorus compound, and a nitrogen-containing basic compound.), An ultraviolet absorber and / or a flame retardant Can be produced by mixing them with a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder. Further, the polycarbonate resin composition may contain a commonly used nucleating agent, impact modifier, foaming agent, dye / pigment, and the like as long as the object of the present invention is not impaired.
  • the polycarbonate resin composition is a compound represented by the general formula (1) and / or a phosphorus compound represented by the general formula (2), a group 1 element (excluding hydrogen), a group 2 element.
  • a group 1 element excluding hydrogen
  • a group 2 element a group 1 element (excluding hydrogen)
  • at least one basic compound selected from the group consisting of the above compounds, basic boron compounds, basic phosphorus compounds and nitrogen-containing basic compounds is not included, or the content of such components is low even if included Can add these compounds suitably, and can mix with the ultraviolet absorber and / or a flame retardant with the said mixer, and can manufacture the polycarbonate resin composition of this invention.
  • Hue (Plate YI) A plate having a thickness of 3 mm, a length of 60 mm, and a width of 60 mm was injection molded under the conditions of a barrel temperature of 280 ° C. and a mold temperature of 90 ° C. using an injection molding machine (manufactured by Nippon Steel Works, J100SS-2).
  • the tristimulus value XYZ which is the absolute value of the color, was measured with a color tester (SC-1-CH, manufactured by Suga Test Instruments Co., Ltd.), and the YI value, which is an index of yellowness, was determined by Calculated. The larger this YI value, the more yellow it is colored.
  • Hue (pellet YI) The hue of the polycarbonate resin pellet was evaluated by measuring the YI value (yellow index value) in the reflected light of the polycarbonate resin pellet according to ASTM D1925.
  • the apparatus used was a spectrocolorimeter (CM-5) manufactured by Konica Minolta. As measurement conditions, a measurement diameter of 30 mm and SCE were selected. Place the calibration glass for petri dish measurement (CM-A212) in the measurement part, and then put the zero calibration box (CM-A124) on it to perform zero calibration, and then perform white calibration using the built-in white calibration plate. It was.
  • CM-A210 white calibration plate
  • L * is 99.40 ⁇ 0.05
  • a * is 0.03 ⁇ 0.01
  • b * is ⁇ 0.43 ⁇ 0.01
  • YI was found to be ⁇ 0.58 ⁇ 0.01.
  • the hue of the pellets was measured by packing the pellets to a depth of about 40 mm in a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm. After taking out the pellet from the glass container, the operation of performing the measurement again was repeated twice, and the average value of the measurement values of three times in total was used. The smaller the YI value, the less yellow the resin is, and the better the color tone.
  • Liquid chromatography and measurement conditions are as follows. Liquid chromatography: LC-10AD manufactured by Shimadzu Corporation Column: YMC PACK ODS-AM M-307-3, 4.6 mm ID ⁇ 75 mm L, Detector: UV280nm, Eluent: (A) 0.05 vol% trifluoroacetic acid aqueous solution, and (B) methanol, Gradient conditions: 0 minutes (B is 40% by volume), 25 minutes (B is 95% by volume), The contents of the compounds represented by the general formulas (3), (4), (5), (6) and (7) were calculated from the respective peak areas based on a calibration curve prepared with bisphenol A.
  • Terminal hydroxyl group concentration 0.1 g of polycarbonate resin was dissolved in 10 ml of methylene chloride, and 5 ml of 5 volume% methylene chloride solution of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) and titanium tetrachloride (Wako Pure Chemical) Color was developed by adding 10 ml of a 2.5% by volume methylene chloride solution manufactured by Kogyo Co., Ltd. (special grade reagent), and the absorbance at a wavelength of 546 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “UV160 type”). .
  • the extinction coefficient was determined using a methylene chloride solution of dihydric phenol used during resin production, and the terminal hydroxyl group concentration in the sample was quantified.
  • the first vertical stirring reactor 6a in which the raw material mixed melt is controlled to be within the range of ⁇ 5% of the reaction liquid temperature and the internal pressure through the raw material introduction pipe heated to 155 ° C. It was continuously fed into.
  • the flow rate was set so that the theoretically produced polymer amount was 75 kg / hr.
  • the liquid level is kept constant while controlling the opening of a valve (not shown) provided in the polymer discharge line at the bottom of the vessel so that the average residence time of the first vertical stirring reactor 6a is 48 minutes. It was.
  • a phenol aqueous solution of triphenylphosphine and cesium carbonate as a catalyst from the catalyst supply port 1d into the first vertical stirring reactor 6a (the ratio of phenol to water is a volume ratio). 90/10) was continuously supplied at a ratio of 200 ⁇ mol of triphenylphosphine and 0.2 ⁇ mol of cesium carbonate with respect to 1 mol of the dihydroxy compound.
  • the polymerization reaction liquid discharged from the bottom of the first vertical stirring reactor 6a is successively transferred to the second vertical stirring reactor 6b, the third horizontal stirring reactor 6c, and the fourth horizontal stirring reactor 6d. Continuously supplied. During the polymerization reaction, the liquid level of each reactor was controlled so that the average residence time shown in Table 1 was obtained.
  • the molten polycarbonate resin extracted from the fourth horizontal stirring reactor 6d was transferred to the twin screw extruder 15a by the gear pump 4c.
  • Example 1-2 The catalyst was a phenol aqueous solution of triphenylphosphine and calcium acetate (the ratio of phenol to water was 90/90 by volume), and the supply amount was 200 ⁇ mol of triphenylphosphine and 1 ⁇ mol of calcium acetate with respect to 1 mol of the dihydroxy compound. Except for this, the same procedure as in Example 1-1 was performed.
  • Example 1-3 116.71 g (about 0.51 mol) of BPA and 116.09 (about 0.54 mol) of BPA were charged into a 150 ml glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure regulator. A mixture was prepared by adding a phenol aqueous solution of triphenylphosphine and cesium carbonate as a catalyst to a ratio of 100 ⁇ mol of triphenylphosphine and 0.15 ⁇ mol of cesium carbonate with respect to 1 mol of the dihydroxy compound.
  • the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off the phenol.
  • the amount of phenol distilled off was measured over time from the start of decompression.
  • the temperature outside the reactor is raised to 250 ° C., and the pressure inside the reactor is reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes, and the distilled phenol is removed from the system. Removed.
  • the temperature outside the reactor was raised to 280 ° C., and the absolute pressure in the reactor was reduced to 30 Pa (about 0.2 Torr) to carry out a polycondensation reaction.
  • the polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power.
  • the inside of the reactor is restored to an absolute pressure of 101.3 kPa with nitrogen and increased to 0.2 MPa with a gauge pressure, and the polycarbonate resin is drawn out in the form of a strand from the bottom of the reactor tank. Got. Then, it pelletized using the rotary cutter.
  • Example 1-4 The same procedure as in Example 1-3 was performed, except that the amount of catalyst added was 200 ⁇ mol triphenylphosphine and 0.2 ⁇ mol cesium carbonate with respect to 1 mol of the dihydroxy compound.
  • Example 1-5 The same procedure as in Example 1-3 was performed, except that the amount of catalyst added was 10 ⁇ mol triphenylphosphine and 0.1 ⁇ mol cesium carbonate with respect to 1 mol of the dihydroxy compound.
  • Example 1-6 The same procedure as in Example 1-3 was performed except that the catalyst was an aqueous phenol solution of triphenylphosphine and calcium acetate, and the addition amount was 100 ⁇ mol triphenylphosphine and 0.5 ⁇ mol calcium acetate with respect to 1 mol of the dihydroxy compound.
  • Example 1-7 The same procedure as in Example 1-3 was performed, except that the catalyst was a phenol aqueous solution of triphenylphosphine and calcium acetate, and the addition amount was 200 ⁇ mol of triphenylphosphine and 0.5 ⁇ mol of calcium acetate with respect to 1 mol of the dihydroxy compound.
  • Example 1-8 The same procedure as in Example 1-3 was performed, except that the catalyst was a phenol aqueous solution of triphenylphosphine and calcium acetate, and the addition amount was 10 ⁇ mol of triphenylphosphine and 0.5 ⁇ mol of calcium acetate with respect to 1 mol of the dihydroxy compound.
  • Example 1-9 The same procedure as in Example 1-3 was performed except that the catalyst was an aqueous phenol solution of triphenylphosphine and potassium carbonate, and the addition amount was 100 ⁇ mol triphenylphosphine and 0.1 ⁇ mol potassium carbonate with respect to 1 mol of the dihydroxy compound.
  • the catalyst was an aqueous phenol solution of tris (4-methoxyphenyl) phosphine and potassium carbonate, and the addition amount was 100 ⁇ mol of tris (4-methoxyphenyl) phosphine and 0.1 ⁇ mol of potassium carbonate with respect to 1 mol of the dihydroxy compound.
  • the addition amount was 100 ⁇ mol of tris (4-methoxyphenyl) phosphine and 0.1 ⁇ mol of potassium carbonate with respect to 1 mol of the dihydroxy compound.
  • Example 1-3 As in Example 1-3.
  • Example 1-11 Implemented except that the catalyst was a phenol aqueous solution of tris (4-methoxyphenyl) phosphine and potassium acetate, and the addition amount was 100 ⁇ mol of tris (4-methoxyphenyl) phosphine and 0.2 ⁇ mol of potassium acetate with respect to 1 mol of the dihydroxy compound.
  • the catalyst was a phenol aqueous solution of tris (4-methoxyphenyl) phosphine and potassium acetate, and the addition amount was 100 ⁇ mol of tris (4-methoxyphenyl) phosphine and 0.2 ⁇ mol of potassium acetate with respect to 1 mol of the dihydroxy compound.
  • the catalyst was a phenol aqueous solution of tris (4-methoxyphenyl) phosphine and potassium acetate, and the addition amount was 100 ⁇ mol of tris (4-methoxyphenyl) phosphine and 0.2 ⁇ mol of potassium acetate with respect
  • Example 1-1 The same procedure as in Example 1-1 was performed except that the catalyst was only an aqueous solution of cesium carbonate and the supply amount was 0.6 ⁇ mol of cesium carbonate with respect to 1 mol of the dihydroxy compound.
  • Example 1-2 The same procedure as in Example 1-3 was performed except that the catalyst was only an aqueous solution of cesium carbonate and the addition amount was 0.5 ⁇ mol with respect to 1 mol of the dihydroxy compound.
  • Example 1-3 The same procedure as in Example 1-3 was performed, except that the catalyst was only an aqueous solution of sodium carbonate and the addition amount was 0.5 ⁇ mol with respect to 1 mol of the dihydroxy compound.
  • Example 1-4 The same procedure as in Example 1-3 was performed, except that the catalyst was only an aqueous solution of calcium acetate in calcium acetate and the addition amount was 2.0 ⁇ mol with respect to 1 mol of the dihydroxy compound.
  • Example 1-5 The same procedure as in Example 1-3 was performed, except that the catalyst was triphenylphosphine alone and the addition amount was 10 ⁇ mol with respect to 1 mol of the dihydroxy compound.
  • Example 2-1 Triphenylphosphine as a catalyst was added to 181.8 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA) and 157.7 kg of diphenyl carbonate (DPC) so as to be 50 ⁇ mol per mol of dihydroxy compound, and further cesium carbonate An aqueous solution was added so that cesium carbonate was 2.0 ⁇ mol per mol of the dihydroxy compound to prepare a mixture. Next, the mixture was charged into a first reactor having an internal volume of 400 L (liter) equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • DPC diphenyl carbonate
  • the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated 10 times to replace the inside of the first reactor with nitrogen.
  • the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture.
  • This molten mixture was then transferred to the second reactor.
  • a 400 L reactor having an agitator, a heat medium jacket, a vacuum pump, and a reflux condenser was used. The inside of the reactor was rotated at 60 rpm, and the temperature inside the heating medium jacket was controlled to keep the inner temperature of the second reactor at 220 ° C.
  • the pressure in the first reactor is increased from 101.3 kPa (760 Torr) to 13.3 kPa in absolute pressure while distilling off phenol by-produced by the oligomerization reaction of BPA and DPC performed in the second reactor.
  • the pressure was reduced to (100 Torr).
  • the second reactor was stirred at 30 rpm, the internal temperature was raised with a heating medium jacket, and the pressure inside the second reactor was reduced from 101.3 kPa to 13.3 kPa in absolute pressure. Thereafter, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure, and the distilled phenol was removed from the system. Further, the temperature was continuously increased, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the polycondensation reaction was performed while maintaining 70 Pa. At that time, the rotation speed of stirring was 10 rpm according to the stirring power, and the final internal temperature in the second reactor was 285 ° C. The polycondensation reaction was completed when the stirrer of the second reactor had a predetermined stirring power determined in advance.
  • the obtained polycarbonate resin was extracted in a strand form from the bottom valve of the second reactor, cooled by passing through a water bath, and then cut into pellets by a cutter.
  • the pellet was cut with a cutter to obtain a polycarbonate resin composition pellet.
  • Table 2-1 together with the results of Examples 2-2 to 2-7 and Compar
  • Example 2-1 except that the types and amounts of the phosphorus compound as a catalyst supplied to the first reactor and the compound having a metal element are shown in Table 2-1, Similarly, a polycondensation reaction of 2,2-bis (4-hydroxyphenyl) propane (BPA) and diphenyl carbonate (DPC) was performed in the first reactor and the second reactor. The obtained polycarbonate resin was extracted in a strand form from the bottom valve of the second reactor, cooled by passing through a water bath, and then cut into pellets by a cutter.
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • DPC diphenyl carbonate
  • Example 2-1 a polycondensation reaction was carried out in the same manner as in Example 2-1, except that a phosphorus compound (triphenylphosphine) as a catalyst supplied to the first reactor was not used, and polycarbonate resin pellets and polycarbonate resin were used. Composition pellets were obtained.
  • a phosphorus compound triphenylphosphine
  • Example 5 polycarbonate resin composition pellets were obtained in the same manner as in Example 5 except that no ultraviolet absorber was added to the obtained polycarbonate resin pellets.
  • Example 3-1 Triphenylphosphine as a catalyst was added to 181.8 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA) and 157.7 kg of diphenyl carbonate (DPC) so as to be 50 ⁇ mol per mol of dihydroxy compound, and further cesium carbonate. An aqueous solution was added so that cesium carbonate was 0.2 ⁇ mol per 1 mol of the dihydroxy compound to prepare a mixture. Next, the mixture was charged into a first reactor having an internal volume of 400 L equipped with a stirrer, a heating medium jacket, a vacuum pump and a reflux condenser.
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • DPC diphenyl carbonate
  • the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated 10 times to replace the inside of the first reactor with nitrogen.
  • the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture.
  • This molten mixture was then transferred to the second reactor.
  • a 400 L reactor having an agitator, a heat medium jacket, a vacuum pump, and a reflux condenser was used. The inside of the reactor was rotated at 60 rpm, and the temperature in the heat medium jacket was controlled to keep the internal temperature of the second reactor at 220 ° C.
  • the pressure in the first reactor is increased from 101.3 kPa (760 Torr) to 13.3 kPa in absolute pressure while distilling off phenol by-produced by the oligomerization reaction of BPA and DPC performed in the second reactor.
  • the pressure was reduced to (100 Torr).
  • the second reactor was stirred at 30 rpm, the internal temperature was raised with a heating medium jacket, and the pressure inside the second reactor was reduced from 101.3 kPa to 13.3 kPa in absolute pressure. Thereafter, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure, and the distilled phenol was removed from the system. Further, the temperature was continuously increased, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the polycondensation reaction was performed while maintaining 70 Pa. At that time, the rotation speed of stirring was 10 rpm according to the stirring power, and the final internal temperature in the second reactor was 285 ° C. The polycondensation reaction was completed when the stirrer of the second reactor had a predetermined stirring power determined in advance.
  • the obtained polycarbonate resin was extracted in a strand form from the bottom valve of the second reactor, cooled by passing through a water bath, and then cut into pellets by a cutter.
  • 2 ppm of butyl p-toluenesulfonate and 60 ppm of flame retardant (potassium diphenylsulfone-3-sulfonate, manufactured by Arichem, trade name “KSS-FR”) were added. It is melt-kneaded in an extruder (TEX-35 ⁇ ), extruded in a strand form from the outlet of a single screw extruder, cooled and solidified with water, then cut and pelletized with a rotary cutter, and a polycarbonate resin composition pellet is obtained. Obtained.
  • Table 3-1 The results of evaluating this polycarbonate resin composition are shown in Table 3-1 together with the results of Examples 3-2 to 3-6 and Comparative Examples 3-1 and 3-2. It is shown in Table 1.
  • Example 3-1 is the same as Example 3-1 except that the types and amounts of the phosphorus compound and the metal element-containing compound as the catalyst supplied to the first reactor are those shown in Table 3-1.
  • the polycondensation reaction of 2,2-bis (4-hydroxyphenyl) propane (BPA) and diphenyl carbonate (DPC) was performed in the first reactor and the second reactor.
  • the obtained polycarbonate resin was extracted in a strand form from the bottom valve of the second reactor, cooled by passing through a water bath, and then cut into pellets by a cutter.
  • Example 3-1 In Example 3-1, this was carried out except that the phosphorus compound (triphenylphosphine) as a catalyst to be supplied to the first reactor was not used, and that the cesium carbonate aqueous solution was used in an amount of 0.5 ⁇ mol per 1 mol of dihydroxy compound. Polycondensation reaction was performed in the same manner as in Example 3-1, to obtain polycarbonate resin pellets and polycarbonate resin composition pellets.
  • the phosphorus compound triphenylphosphine
  • Example 3-5 polycarbonate resin composition pellets were obtained in the same manner as in Example 3-5, except that no flame retardant was added to the obtained polycarbonate resin pellets.
  • the polycarbonate resin composition of the present invention has a good hue, excellent properties such as transparency, heat resistance, mechanical strength and impact resistance, and various mechanical parts, various electrically insulating materials, and automobile parts. It can be used for various applications such as information equipment materials such as optical disks and safety protection materials such as helmets.
  • information equipment materials such as optical disks
  • safety protection materials such as helmets.

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JP7447641B2 (ja) * 2020-04-02 2024-03-12 三菱ケミカル株式会社 ポリカーボネート樹脂組成物及びその成形品
CN115791662A (zh) * 2022-12-15 2023-03-14 四川中蓝国塑新材料科技有限公司 一种检测聚碳酸酯中末端羟基值含量的建立与测定方法

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