WO2017150276A1 - ポリカーボネート樹脂及びその製造方法 - Google Patents
ポリカーボネート樹脂及びその製造方法 Download PDFInfo
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- WO2017150276A1 WO2017150276A1 PCT/JP2017/006384 JP2017006384W WO2017150276A1 WO 2017150276 A1 WO2017150276 A1 WO 2017150276A1 JP 2017006384 W JP2017006384 W JP 2017006384W WO 2017150276 A1 WO2017150276 A1 WO 2017150276A1
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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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
- C08G64/1616—Aliphatic-aromatic or araliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
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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
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
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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
- C08G64/42—Chemical after-treatment
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- 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
- C08K5/02—Halogenated hydrocarbons
Definitions
- the present invention relates to a polycarbonate resin having high fluidity and capable of reducing mold dirt such as mold deposit.
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is less than 1% by mass, the fluidity is high, and mold contamination such as mold deposit is reduced.
- the present invention relates to a simple method for producing a polycarbonate resin.
- PC Polycarbonate
- a high quality PC is required from the viewpoint of improvement in transferability, durability of a recording film, long-term reliability of the PC substrate itself, etc. due to less stamper contamination during substrate production. .
- Patent Document 1 forms a reaction mixture while blowing phosgene into bisphenol, and adds a quaternary ammonium salt to the reaction mixture to give a predetermined
- a molecular weight regulator terminal terminator
- the amount of low molecular weight carbonate compounds and polycarbonate oligomers in the polycarbonate resin is small, and high flow for optical recording media that hardly causes deposits on the stamper. It has been proposed to obtain a conductive polycarbonate resin.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2001-208917 proposes to use polycarbonate having excellent fluidity and mechanical strength for the light guide plate.
- JP-A-8-325369 (Patent Document 4) and JP-A-2002-105190 (Patent Document 5) reduce the amount of low-molecular-weight carbonate compounds having a molecular weight of 1,000 or less contained in a polycarbonate resin. A method is disclosed.
- polycarbonate resin used for the manufacture of complicated and thinned products is required not only to prevent mold contamination as described above but also to have high fluidity.
- the polycarbonates described in Patent Documents 2 and 3 are polycarbonates having excellent fluidity, but there is no description about the amount of the low molecular weight carbonate compound in the polycarbonate resin, which is required when manufacturing complicated and thin products. There is a fear that the mold stain prevention property is not sufficient.
- Patent Documents 4 and 5 describe a method for reducing the amount of the low molecular weight carbonate compound in the polycarbonate resin, but the method described in Patent Document 4 requires removing a part of the aqueous phase after the reaction. There are many processes and complicated.
- the method described in Patent Document 5 requires addition of a quaternary ammonium salt after completion of the phosgene blowing, and after addition of the polymer to a predetermined molecular weight, it is necessary to add a molecular weight regulator, that is, a terminal terminator.
- a molecular weight regulator that is, a terminal terminator.
- the present inventors have now provided a polycarbonate resin having a specific terminal structure and a specific viscosity average molecular weight, and having a content of a low molecular weight carbonate compound of less than 1% by mass. If so, it was found that the fluidity is high and mold contamination such as mold deposit can be reduced.
- the present inventors have now conducted an interfacial polymerization reaction using a terminal stopper solution containing a terminal stopper having a specific structure at a predetermined concentration.
- the polycarbonate resin contains less than 1% by mass of a low molecular weight carbonate compound having a molecular weight of 1,000 or less, has high fluidity, and can reduce mold stains such as mold deposits. The knowledge that the resin can be easily produced was obtained.
- the present invention is based on these findings.
- R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms
- r represents an integer of 1 to 5.
- Each of the substituents is independently halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
- X represents a structure selected from the group consisting of a single bond, —O—, —S—, —SO—, —SO 2 —, —CO—, and the following general formulas (3) to (6). )
- R 14 and R 15 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms, or a substituent.
- R 16 and R 17 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 5 carbon atoms.
- Each of R 16 and R 17 is bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms;
- Each of the substituents is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 18 to R 21 are each independently hydrogen, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 5 carbon atoms which may have a substituent.
- Each of the substituents is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 22 to R 31 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- X in the general formula (2) has a structure represented by the general formula (3).
- the terminal structure represented by the general formula (1) has a structure represented by the following general formula (7), (8) or (9), according to any one of [1] to [4] Polycarbonate resin.
- R 33 is an alkyl group having 5 to 14 carbon atoms.
- R 32 is an alkyl group having 1 to 22 carbon atoms.
- R 34 is an alkyl group having 1 to 23 carbon atoms.
- R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms
- r represents an integer of 1 to 5.
- a method for producing a polycarbonate resin comprising a step of adding a terminal stopper solution containing the terminal stopper at a concentration of less than 10% by mass to a solution containing the dihydric phenol.
- the method according to [7], comprising a step of blowing phosgene into the solution containing the dihydric phenol before the step of adding the terminal stopper solution.
- the terminal stopper solution is selected from the group consisting of methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, trichloroethane, dichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, acetophenone, cyclohexane and anisole.
- the method according to [7] or [8], comprising a solvent.
- Each of the substituents is independently halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
- X represents a structure selected from the group consisting of a single bond, —O—, —S—, —SO—, —SO 2 —, —CO—, and the following general formulas (3) to (6). )
- R 14 and R 15 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms, or a substituent.
- R 16 and R 17 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 5 carbon atoms.
- Each of R 16 and R 17 is bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms;
- Each of the substituents is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 18 to R 21 are each independently hydrogen, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 5 carbon atoms which may have a substituent.
- Each of the substituents is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 22 to R 31 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- X in the general formula (2a) has a structure represented by the general formula (3).
- the compound represented by the general formula (2a) is 2,2-bis (4-hydroxyphenyl) propane.
- the terminal terminator is a compound represented by the following general formula (7a), (8a) or (9a).
- R 33 is an alkyl group having 5 to 14 carbon atoms.
- R 32 is an alkyl group having 1 to 22 carbon atoms.
- R 34 is an alkyl group having 1 to 23 carbon atoms.
- R 33 in the general formula (7a) is, n- octyl group, iso - octyl group, selected from the group consisting of t- octyl group and dodecyl group, either one or more, according to [15] Method.
- the polycarbonate resin according to the present invention has high fluidity and can reduce mold contamination such as mold deposit. According to the method for producing a polycarbonate resin according to the present invention, the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is less than 1% by mass, the fluidity is high, and the mold A polycarbonate resin capable of reducing mold contamination such as deposit can be easily produced.
- the first aspect includes, for example, the following inventions.
- R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms
- r represents an integer of 1 to 5.
- the above invention will be described in detail below.
- the polycarbonate resin according to the present invention has a terminal structure represented by the following general formula (1) and has a viscosity average molecular weight of 10,000 to 18,000. Furthermore, the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is less than 1% by mass.
- R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms, and r is an integer of 1 to 5) Represents.
- the terminal structure represented by the general formula (1) has a structure represented by the following general formula (7), (8) or (9).
- R 33 is an alkyl group having 5 to 14 carbon atoms.
- R 32 is an alkyl group having 1 to 22 carbon atoms.
- R 34 is an alkyl group having 1 to 23 carbon atoms.
- R 32 , R 33 and R 34 in the general formulas (7), (8) and (9) are each composed of an n-octyl group, an iso-octyl group, a t-octyl group and a dodecyl group.
- One or more of the groups are each composed of an n-octyl group, an iso-octyl group, a t-octyl group and a dodecyl group.
- R 6 to R 13 are each independently hydrogen, halogen, an optionally substituted alkoxyl group having 1 to 5 carbon atoms, or an optionally substituted alkyl group having 1 to 20 carbon atoms.
- an alkoxy group having 1 to 5 carbon atoms which may have a substituent an aryl group having 6 to 12 carbon atoms which may have a substituent, and an aryl group having 7 to 17 carbon atoms which may have a substituent
- R 14 and R 15 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 5 carbon atoms.
- An aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and 7 to 17 carbon atoms which may have a substituent Represents any one of the group consisting of aralkyl groups, and each substituent is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms; c represents an integer of 1 to 20.
- R 16 and R 17 are each independently hydrogen, halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 5 carbon atoms.
- Each of R 16 and R 17 is bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, and each substituent is independently halogen, (It is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
- R 18 to R 21 are each independently hydrogen, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 5 carbon atoms which may be
- An alkoxy group, an aryl group having 6 to 12 carbon atoms that may have a substituent, an alkenyl group having 2 to 5 carbon atoms that may have a substituent, and a carbon number having 7 to 17 that may have a substituent Or R 18 and R 19 and R 20 and R 21 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms,
- the substituents are each independently halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)
- R 22 to R 31 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin according to the present invention is less than 1% by mass.
- the low molecular weight carbonate compound having a molecular weight of 1,000 or less includes, for example, a dicarbonate compound that is a condensation reaction product of a dihydric phenol dichloroformate and a terminal terminator generated by a phosgenation reaction of a dihydric phenol. It is.
- Polycarbonate resins containing a large amount of low molecular weight carbonate compounds with a molecular weight of 1,000 or less are molds (molds) at relatively early stages when injection molding of discs and complicated and thin products is performed continuously. ) Tends to be contaminated by a small amount of deposits (mold deposits). In this respect, if the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less is less than 1% by mass, the contamination of the mold is effectively prevented.
- the lower limit of the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is preferably about 0.01% by mass in view of the purification cost.
- the polycarbonate resin according to the present invention is obtained by performing polymerization using a dihydric phenol and a carbonate ester-forming compound and stopping the reaction with a terminal stopper. Each raw material will be described below.
- the divalent phenol used to produce the polycarbonate resin of the present invention is not particularly limited as long as it is a phenolic compound having two hydroxyl groups in the molecule, but the resulting molded article has high impact resistance and high purity,
- a dihydric phenol represented by the following general formula (2a) is preferable from the viewpoint of a large circulation amount.
- the obtained polycarbonate resin has a structural unit represented by the general formula (2).
- R 6 to R 13 are each independently hydrogen, halogen, an optionally substituted alkoxyl group having 1 to 5 carbon atoms, or an optionally substituted alkyl group having 1 to 20 carbon atoms.
- an alkoxy group having 1 to 5 carbon atoms which may have a substituent an aryl group having 6 to 12 carbon atoms which may have a substituent, and an aryl group having 7 to 17 carbon atoms which may have a substituent
- Examples of the dihydric phenol represented by the general formula (2a) include 2,2-bis (4-hydroxyphenyl) propane (BPA), 1,1-bis (4-hydroxyphenyl) ethane, bis (4 -Hydroxyphenyl) methane, bis (4-hydroxyphenyl) -p-diisopropylbenzene, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diphenylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,
- BPA 2,2-bis (4-hydroxyphenyl) propane
- 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) ethane
- bis (4-hydroxyphenyl) methane are more preferable, and stability as a monomer
- BPA 2,2-bis (4-hydroxyphenyl) propane
- BPA is particularly preferable from the viewpoint that it is easy to obtain a product containing a small amount of impurities.
- the polycarbonate resin of the present invention may have a branched structure as necessary.
- phloroglucin 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4- Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris
- a polyhydroxy compound represented by (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole ( isatin bisphenol), 5-chlorouisatin bisphenol, 5,7-dichloro Bivalent phenols described above, which are polyfunctional compounds represented byucisatin bisphenol, 5-bromoisatin bisphenol, etc. It may be used to replace as part.
- Carbonate forming compound examples include phosgene, triphosgene, carbonic acid diester, and a carbonyl compound.
- phosgene is particularly preferable from the viewpoint of quality such as hue and stability of the obtained resin, and cost.
- Examples of the carbonyl compound include carbon monoxide and carbon dioxide.
- Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate.
- a diaryl carbonate compound is mentioned.
- diphenyl carbonate and substituted diphenyl carbonates such as di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate are reactive, the hue of the resulting resin, and further from the viewpoint of cost.
- diphenyl carbonate can be used alone or in admixture of two or more.
- the terminal terminator used for the production of the polycarbonate resin of the present invention is a monohydric phenol represented by the following general formula (1a).
- R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms, and r is 1 to Represents an integer of 5.
- terminal terminator represented by the general formula (1a) include pentylphenol, hexylphenol, heptylphenol, n-octylphenol, iso-octylphenol, t-octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol.
- Hydroxybenzoic acid esters such as hydroxybenzoic acid 2-ethylhexyl ester, hydroxybenzoic acid 2-hexyldecyl ester, hydroxybenzoic acid hexadecyl ester, and hydroxybenzoic acid docosyl ester, and ethoxyphenol, hexyloxyphenol, n-octyloxyphenol, iso-octyloxyphenol, t-octyloxyphenol, dodecyloxyphenol Any or more of alkoxyphenols such as docosyloxyphenol can be used as the end terminator.
- terminal terminator represented by the general formula (1a) is more preferably one represented by the general formula (7a), (8a) or (9a).
- R 33 is an alkyl group having 5 to 14 carbon atoms.
- R 32 is an alkyl group having 1 to 22 carbon atoms.
- R 34 is an alkyl group having 1 to 23 carbon atoms.
- terminal terminator represented by the general formula (7a), (8a) or (9a) include parapentylphenol, parahexylphenol, paraheptylphenol, para-n-octylphenol, para-iso-octylphenol, Alkylphenols such as para-t-octylphenol, paranonylphenol, paradecylphenol, paradodecylphenol, and paratetradecylphenol, parahydroxybenzoic acid 2-ethylhexyl ester, parahydroxybenzoic acid 2-hexyldecyl ester, parahydroxybenzoic acid hexa Decyl esters, and hydroxybenzoic acid esters such as parahydroxybenzoic acid docosyl ester, and para-ethoxyphenol, para-hexyloxyphenol, para-n-octy Any or more alkoxyphenols such as ruoxyphenol, para-iso-octyloxyphenol, para-t-octyloxy
- a terminal group that remains a phenolic OH group that does not react with the terminal stopper may be formed.
- This phenolic OH group is preferably as small as possible from the viewpoint of hydrolysis resistance.
- 80 mol% or more of all terminals are preferably sealed with a structure represented by the general formula (1), and 90 mol% or more of all terminals are represented by the general formula (1). It is particularly preferred that the structure is sealed.
- the terminal stopper used in the present invention may be used in combination of two or more kinds within the range not departing from the gist of the present invention depending on the required properties for the material, and is used in combination with a structure other than the structure represented by the general formula (1a) It is permissible.
- End terminators that may be used in combination include phenol, p-cresol, o-cresol, 2,4-xylenol, pt-butylphenol, o-allylphenol, p-allylphenol, p-hydroxystyrene, p- Alkylphenols such as hydroxy- ⁇ -methylstyrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, eugenol, palmitylphenol, stearylphenol, and behenylphenol;
- Examples include parahydroxybenzoic acid alkyl esters such as methyl ester, ethyl ester, propyl ester, butyl ester, amyl ester, hexyl ester, and heptyl ester of parahydroxybenzoic acid.
- a terminal terminator that may be used in combination is pt-butylphenol from the viewpoints of purity and cost.
- another terminal terminator it is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total terminal terminator.
- the molecular weight of the polycarbonate resin of the present invention is controlled by the amount of the end stopper used.
- the degree of polymerization of the dihydric phenol used for the main skeleton and the amount of the terminal terminator used are shown in the following mathematical formula (I).
- the usage amounts of the terminal terminator (monohydric phenol) and the dihydric phenol are determined, but the preferred range of the usage amount (mol) of the dihydric phenol: the usage amount (mol) of the terminal terminator is 50. 1 to 4: 1, more preferably in the range of 40: 1 to 4: 1, more preferably 23: 1 to 4: 1, still more preferably 20: 1 to 6: 1, More preferably, it is 16: 1 to 6: 1, and particularly preferably 15: 1 to 8: 1.
- the polycarbonate resin of the present invention is allowed to be mixed with other resins and various additives within the range not departing from the gist of the present invention due to the required properties for the material.
- the polycarbonate resin of the present invention may contain other resins as necessary.
- other resins include heat such as polycarbonate resin other than the polycarbonate resin used in the present invention, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin).
- Plastic polyester resin polystyrene resin (PS resin), high impact polystyrene resin (HIPS), styrene resin such as acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin); methyl methacrylate- Core / shell type elastomer such as acrylic rubber-styrene copolymer (MAS), elastomer such as polyester elastomer; cyclic cycloolefin resin (COP resin), cyclic cycloolefin (COP) copolymer Polyolefin resin such as fat; Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin) ); Polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); polycaprolact
- Particularly preferred mixed resins include PS resin, AS resin, and PMMA resin.
- the component ratio of the other resin in the polycarbonate resin of the present invention is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total resin components. Various physical properties can be maintained by setting the component ratio of the other resin to 10% by mass or less.
- additives may be added to the polycarbonate resin of the present invention without departing from the gist of the present invention.
- the additive include at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant.
- an antistatic agent, a fluorescent whitening agent, an antifogging agent, a fluidity improving agent, a plasticizer, a dispersing agent, an antibacterial agent and the like may be added as long as desired physical properties are not significantly impaired.
- heat stabilizers include phenol-based, phosphorus-based, and sulfur-based heat stabilizers.
- phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid
- acidic metal pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, calcium acid pyrophosphate; potassium potassium phosphate , Sodium phosphate, cesium phosphate, zinc phosphate, etc., group 1 or group 10 metal phosphates
- organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid
- acidic metal pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, calcium acid pyrophosphate
- potassium potassium phosphate Sodium phosphate, cesium phosphate,
- a phosphite compound (a), phosphorous acid (b) and tetrakis esterified with at least one ester in the molecule esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms There may be mentioned at least one selected from the group of (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).
- phosphite compound (a) examples include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris (monononylphenyl) phos Phyto, Tris (monononyl / dinonyl phenyl) phosphite, Trisnonyl phenyl phosphite, Tris (octylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, Trinonyl phosphite, Didecyl Monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite,
- organic phosphite compound examples include, for example, “ADK STAB 1178”, “ADK STAB 2112”, “ADK STAB HP-10”, “ADK STAB PEP-36”, manufactured by ADEKA Corporation (Johoku Chemical). Examples thereof include “JP-351”, “JP-360”, “JP-3CP” manufactured by Kogyo Co., Ltd., “Irgaphos 168” manufactured by BASF, and the like.
- Examples of phosphoric acid stabilizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like. it can.
- 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.
- the addition ratio of the heat stabilizer is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, with respect to 100 parts by mass of the polycarbonate resin. Moreover, it is 1 mass part or less, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.
- antioxidants examples include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and the like. Specifically, 2,6-di-tert-butyl-4-methylphenol, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, n-octadecyl-3- (3 ′, 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis ⁇ 2- [3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1
- phenolic antioxidants include, for example, “Irganox 1010” (registered trademark, the same shall apply hereinafter) manufactured by BASF, Irganox 1076 “, ADEKA Co., Ltd.” STAB AO-50 “, and the like can be given” ADK STAB AO-60 ".
- 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.
- the addition ratio of the antioxidant is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and 1 part by mass or less, preferably 0 with respect to 100 parts by mass of the polycarbonate resin. .5 parts by mass or less. If the addition ratio of the antioxidant is too small, the effect as an antioxidant may be insufficient, and if the addition ratio of the antioxidant is too large, the effect reaches a peak and may not be economical. is there.
- Examples of flame retardants include organic sulfonic acid metal salts.
- the organic sulfonic acid metal salts include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. These may be used alone or in combination of two or more.
- an alkali metal salt and an alkaline-earth metal salt are preferable.
- the alkali metal include sodium, lithium, potassium, rubidium, and cesium.
- Examples of alkaline earth metals include calcium and strontium.
- the preferred metal of the organic sulfonic acid metal salt used in the present invention is an alkali metal such as sodium, potassium, rubidium and cesium, more preferably sodium and potassium. By adopting such a metal, it is possible to effectively promote formation of a carbonized layer during combustion and maintain high transparency.
- the aliphatic sulfonic acid metal salt is preferably a fluoroalkane-sulfonic acid metal salt, more preferably a perfluoroalkane-sulfonic acid metal salt.
- examples of the fluoroalkane-sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, among which alkali metal salts are preferable.
- the carbon number of the fluoroalkanesulfonic acid metal salt is preferably 1 to 8, more preferably 2 to 4. By setting it as such a range, the effect that high transparency can be maintained is acquired.
- preferred fluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, potassium perfluorobutane-sulfonate, perfluoroethane-sodium sulfonate, potassium perfluoroethane-sulfonate, and the like. it can.
- aromatic sulfonic acid metal salt examples include alkali metal salts and alkaline earth metal salts, and alkali metal salts are preferable.
- aromatic sulfonesulfonic acid alkali metal salt examples include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, diphenylsulfone-3-sulfone.
- the organic sulfonic acid metal salt that can be used in the polycarbonate resin according to the present invention is particularly a diphenylsulfone-3-sulfonic acid potassium salt, p-toluenesulfonic acid potassium salt, p, from the viewpoint of improving the transparency of the molded product.
- -Potassium styrenesulfonate and potassium dodecylbenzenesulfonate are preferable, and potassium salt of diphenylsulfone-3-sulfonic acid is more preferable.
- the added mass of the organic sulfonic acid metal salt with respect to 100 parts by mass of the polycarbonate resin is 0.005 parts by mass to 0.1 parts by mass, preferably 0.01 parts by mass to 0.1 parts by mass. Is 0.03 parts by mass to 0.09 parts by mass. Moreover, in this invention, you may mix
- a silicone compound can be added as a flame retardant aid.
- a silicone compound what has a phenyl group in a molecule
- numerator is preferable. By having a phenyl group, the dispersibility of the silicone compound in the polycarbonate is improved, and the transparency and flame retardancy are excellent.
- the mass average molecular weight of the silicone compound is preferably 450 to 5,000, more preferably 750 to 4,000, more preferably 1,000 to 3,000, and particularly preferably 1,500 to 2,500. By making the mass average molecular weight 450 or more, the production becomes easy, the adaptation to industrial production becomes easy, and the heat resistance of the silicone compound is hardly lowered.
- the mass average molecular weight of the silicone compound is 5,000 or less, the dispersibility in the polycarbonate resin is unlikely to decrease, and as a result, the flame retardancy of the molded article and the mechanical properties are more effectively reduced. Tend to be suppressed.
- the addition ratio of the flame retardant aid is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and 7.5 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin. Preferably it is 5 mass parts or less. If the addition rate of the flame retardant aid is too small, the flame retardancy may be insufficient, and if the addition rate of the flame retardant aid is too high, appearance defects such as delamination will occur and transparency will be reduced. The flame retardancy will reach its peak and may not be economical.
- UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide, as well as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, and phenyl salicylates.
- Organic ultraviolet absorbers such as organic compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.
- benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethylbenzyl) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-) Methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′-hydroxy-3 ′ , 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- ( , 1,3,3
- benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy- Benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4 And 4'-tetrahydroxy-benzophenone.
- phenyl salicylate UV absorbers include phenyl salicylate and 4-tert-butyl-phenyl salicylate.
- triazine ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol and the like.
- hindered amine ultraviolet absorber examples include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
- the proportion of the ultraviolet absorber added is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and 3 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin. It is below mass parts. If the addition ratio of the UV absorber is too small, the effect of improving the weather resistance may be insufficient, and if the addition ratio of the UV absorber is too large, a mold deposit or the like is generated in the molded body, and a mold is formed at the time of molding. May cause contamination.
- release agent examples include release agents such as carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin type). Specifically, at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. Can be mentioned.
- the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid.
- the aliphatic carboxylic acid includes an alicyclic carboxylic acid.
- preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable.
- Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid, Examples include glutaric acid, adipic acid, azelaic acid, and the like.
- the same one as the aliphatic carboxylic acid can be used.
- examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable.
- the aliphatic includes alicyclic compounds.
- the alcohol examples include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. be able to.
- said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.
- esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.
- Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
- the alicyclic hydrocarbon is also included in the aliphatic hydrocarbon.
- these hydrocarbon compounds may be partially oxidized.
- paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
- the number average molecular weight is preferably 200 to 5,000.
- aliphatic hydrocarbons may be a single substance or a mixture of components and various molecular weights as long as the main component is within the above range.
- the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.
- the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and 2 parts by mass or less, based on 100 parts by mass of the polycarbonate resin. Preferably it is 1 mass part or less.
- the addition ratio of the mold release agent is too small, the effect of mold release at the time of molding may not be sufficient, and if the addition ratio of the mold release agent is too large, the hydrolysis resistance of the molded product will be reduced, during injection molding. There is a possibility that mold contamination will occur.
- the dye / pigment as a colorant examples include inorganic pigments, organic pigments, and organic dyes.
- inorganic pigments for example, sulfide pigments such as carbon black, cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron -Based brown, titanium-cobalt green, cobalt-green, cobalt-blue, copper-chromium-based black, copper-iron-based black and other oxide pigments; yellow lead, molybdate orange and other chromic pigments; bitumen and other ferrocyanians And pigments.
- organic pigments and organic dyes as colorants, for example, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone And condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl dyes.
- titanium oxide, carbon black, cyanine, quinoline, anthraquinone, phthalocyanine dyes and the like are preferable from the viewpoint of thermal stability.
- 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.
- dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.
- the proportion of the colorant added is, for example, 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin. If the ratio of the colorant added is too large, the impact resistance of the molded product may be insufficient.
- the polycarbonate resin of the present invention can be synthesized based on a known method, but from the viewpoint of suppressing the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less to less than 1% by mass without using an additional purification step. It is preferable to synthesize by an interfacial polymerization method. Alternatively, the polycarbonate resin of the present invention may be synthesized by the method described in the second aspect of the present invention. The second aspect will be described later in this specification.
- the method for producing the polycarbonate resin of the present invention by the interfacial polymerization method will be described in detail below.
- the pH is usually maintained at 10 or higher, and the dihydric phenol is dissolved in the aqueous alkali solution.
- a polycarbonate precursor formed by a phosgenation reaction between phosgene and a dihydric phenol is formed.
- a terminal terminator is added, and a polycondensation reaction is performed by adding a polymerization catalyst such as tertiary amine or quaternary ammonium salt.
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less in the obtained polycarbonate resin can be reduced by dissolving the terminal stopper in a solvent and adding it as a terminal stopper solution.
- concentration of the terminal stopper in the terminal stopper solution is less than 10% by mass
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less in the obtained polycarbonate resin is less than 1% by mass. This is preferable.
- the concentration of the terminal stopper in the terminal stopper solution is more preferably less than 7% by mass, and further preferably less than 5% by mass.
- the low molecular weight carbonate compound having a molecular weight of 1,000 or less is less than 1% by mass, and the viscosity average molecular weight (Mv) of the polycarbonate resin is 10,000 to 18,000. is there. Therefore, the polycarbonate resin has high fluidity and can reduce mold contamination such as mold deposit.
- Phosgene is usually used in an amount of 100 to 120 mol, preferably 105 to 115 mol, per 100 mol of the dihydric phenol.
- carbonyl chloride called phosgene is preferably used, but carbonyl halides other than chlorine can be used without any problem.
- the phosgene blowing time is usually 10 to 120 minutes, preferably 15 to 60 minutes.
- a base is usually used for the reaction between the dihydric phenol and phosgene.
- an alkali metal compound such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal compound is used.
- the equivalent ratio of dihydric phenol and base as described above is preferably 1: 1.1 to 1.6.
- Such a base is usually used in the form of an aqueous solution, and the base concentration in this aqueous solution is usually 6 to 20% by mass.
- the water used here is distilled water, ion-exchanged water, or water recovered when producing polycarbonate.
- sodium sulfite, sodium hydrosulfite, sodium borohydride or the like can be used to prevent oxidative coloring of dihydric phenol.
- an organic solvent is used to facilitate the phosgenation reaction and polymerization reaction.
- the organic solvent used is an organic solvent that is insoluble in water and inert to the reaction, and that can dissolve the polycarbonate produced by the reaction.
- organic solvents include chlorinated aliphatic hydrocarbons such as methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, trichloroethane, and dichloroethane, and chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene.
- chlorinated aliphatic hydrocarbons such as methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, trichloroethane, and dichloroethane
- chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene.
- the addition timing of the end-stopper solution is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction, but it is preferably added following the phosgene blowing step.
- the base added again together with the terminal terminator is necessary to complete the condensation reaction between the terminal terminator and the resin terminal Cl group. If the alkali concentration in the reaction solution becomes too high before the end terminator is added, the reaction between the resin end Cl group and the base occurs frequently, and the resin end becomes an OH group, making it difficult to control the molecular weight and the desired weight. There is a risk that coalescence cannot be obtained. In addition, when the base is not added together with the terminal terminator, there is a possibility that the reaction with the terminal terminator is delayed and the molecular weight of the polymer is excessively increased.
- a polymerization accelerating catalyst after adding a base when adding the terminal terminator.
- the polymerization is completed with stirring for 30 to 120 minutes.
- the polymerization promotion catalyst used in the present invention is a tertiary amine such as triethylamine, a tertiary phosphine, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, or a compound having an amide group. used. Of these, tertiary amines such as triethylamine are preferred.
- the addition amount of the polymerization accelerating catalyst is 0.1 to 10 mmol with respect to 1 mol of the charged dihydric phenol.
- the polycarbonate resin of the present invention is usually produced by a batch method.
- a production apparatus of this batch method a jacketed reaction kettle equipped with a stirrer, a gas blowing pipe and a condenser is used.
- the stirrer is not particularly limited, but an inversion stirrer is preferable.
- the reversal rate is 70 to 200 times / minute when phosgene is blown, and 70 to 230 times / minute from the end-stopper addition to the end of the reaction.
- the reaction temperature is preferably 10 to 25 ° C. when phosgene is blown, and 20 to 35 ° C. from the addition of the end terminator to the end of the reaction.
- the viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is 10,000 to 18,000.
- the viscosity average molecular weight (Mv) is preferably 11,000 to 15,000, more preferably the viscosity average molecular weight (Mv) is 12,000 or more and 14,500.
- the viscosity average molecular weight (Mv) is 10,000 or more, the mechanical strength is improved.
- the viscosity average molecular weight (Mv) is 18,000 or less, the melt viscosity is lowered and the fluidity is improved, and it is easy to form a thin-walled / large-sized molded product. become.
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin of the present invention is evaluated by gel permeation chromatographic analysis performed under the following conditions.
- the melt fluidity of the polycarbonate resin of the present invention is evaluated by a volume flow rate (Q value) measured under the following conditions using a Koka flow tester.
- Q value volume flow rate measured under the following conditions using a Koka flow tester.
- a high Q value indicates a high melt fluidity
- a low Q value indicates a low melt fluidity.
- ⁇ Q value measurement conditions Measuring instrument: Koka type flow tester Load: 160 kgf / cm 2 Orifice: 1mm diameter x 10mm length Measurement temperature: 240 ° C
- CFT-500D manufactured by Shimadzu Corporation can be used.
- the Q value of the polycarbonate resin of the present invention measured under the above measurement conditions is 10 ⁇ 10 ⁇ 2 cc / sec or more, preferably 13 ⁇ 10 ⁇ 2 cc / sec or more, particularly preferably at a measurement temperature of 240 ° C. Is 15 ⁇ 10 ⁇ 2 cc / sec or more, and most preferably 19 ⁇ 10 ⁇ 2 cc / sec or more.
- the Q value is preferably 100 ⁇ 10 ⁇ 2 cc / sec or less, and more preferably 80 ⁇ 10 ⁇ 2 cc / sec or less.
- the Q value is 100 ⁇ 10 ⁇ 2 cc / sec or less, there is a tendency that it is possible to prevent molding defects such as sprue breakage and generation of cavities. By setting it as such a range, a thin and large-sized molded object can be molded.
- the polycarbonate resin of the present invention has higher fluidity than conventional polycarbonate resins and can reduce mold contamination such as mold deposits. It is suitable for light guide plates in the field of light units, various display devices, and lighting devices. Examples of apparatuses using such a light guide plate include mobile terminals such as mobile phones, mobile notebooks, netbooks, slate PCs, tablet PCs, smartphones, tablet terminals, cameras, watches, notebook computers, various displays, and lighting devices. Etc. According to one aspect of the present invention, a light guide plate comprising the polycarbonate resin of the present invention is provided.
- the second aspect includes the following inventions.
- a method for producing a polycarbonate resin comprising a step of adding a terminal stopper solution containing the terminal stopper at a concentration of less than 10% by mass to a solution containing the dihydric phenol.
- the interfacial polymerization reaction there is provided a method for producing a polycarbonate resin, which comprises a step of adding a terminal stopper solution containing a terminal stopper at a concentration of less than 10% by mass to a solution containing a dihydric phenol.
- the present invention is not limited to this method.
- the pH is usually maintained at 10 or higher, and the dihydric phenol is dissolved in the alkaline aqueous solution.
- phosgene carbonic acid ester forming compound
- a polycarbonate precursor formed by a phosgenation reaction between phosgene and a dihydric phenol is formed.
- a polycondensation reaction is performed by adding a terminal stopper solution and adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt.
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less in the obtained polycarbonate resin is less than 1% by mass by adding a terminal terminator solution containing the terminal terminator at a concentration of less than 10% by mass. Can be suppressed.
- the concentration of the terminator in the terminator solution is preferably less than 7% by mass, and more preferably less than 5% by mass.
- the lower limit of the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is preferably about 0.01% by mass in view of the purification cost.
- Phosgene is usually used in an amount of 100 to 140 mol, preferably 100 to 120 mol, more preferably 105 to 115 mol, per 100 mol of the dihydric phenol.
- carbonyl chloride called phosgene is preferably used as the carbonic acid ester forming compound, but the following carbonic acid ester forming compounds other than phosgene can also be suitably used.
- the phosgene blowing time is usually 10 to 120 minutes, preferably 15 to 60 minutes.
- a base is usually used for the reaction between the dihydric phenol and phosgene.
- an alkali metal compound such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal compound is used.
- the equivalent ratio between the dihydric phenol and the base as described above is preferably 1: 1.1 to 2.0, more preferably 1: 1.1 to 1.6.
- Such a base is usually used in the form of an aqueous solution, and the base concentration in this aqueous solution is usually 6 to 20% by mass.
- the water used here is distilled water, ion-exchanged water, or water recovered when producing polycarbonate.
- sodium sulfite, sodium hydrosulfite, sodium borohydride or the like can be used to prevent oxidative coloring of dihydric phenol.
- an organic solvent is used to facilitate the phosgenation reaction and polymerization reaction.
- the organic solvent used is an organic solvent that is insoluble in water and inert to the reaction, and that can dissolve the polycarbonate produced by the reaction.
- organic solvents include chlorinated aliphatic hydrocarbons such as methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, trichloroethane, and dichloroethane, and chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene.
- chlorinated aliphatic hydrocarbons such as methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, trichloroethane, and dichloroethane
- chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene.
- the addition timing of the end-stopper solution is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction, but it is preferably added following the phosgene blowing step.
- the base added again together with the terminal terminator is necessary to complete the condensation reaction between the terminal terminator and the resin terminal Cl group. If the alkali concentration in the reaction solution becomes too high before the end terminator is added, the reaction between the resin end Cl group and the base occurs frequently, and the resin end becomes an OH group, making it difficult to control the molecular weight and the desired weight. There is a risk that coalescence cannot be obtained. In addition, when the base is not added together with the terminal terminator, there is a possibility that the reaction with the terminal terminator is delayed and the molecular weight of the polymer is excessively increased.
- a polymerization accelerating catalyst after adding a base when adding the terminal terminator.
- the polymerization is completed with stirring for 30 to 120 minutes.
- the polymerization promotion catalyst used in the present invention is a tertiary amine such as triethylamine, a tertiary phosphine, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, or a compound having an amide group. used. Of these, tertiary amines such as triethylamine are preferred.
- the addition amount of the polymerization accelerating catalyst is 0.1 to 10 mmol with respect to 1 mol of the charged dihydric phenol.
- the production method of the present invention is usually performed by a batch method.
- a production apparatus of this batch method a jacketed reaction kettle equipped with a stirrer, a gas blowing pipe and a condenser is used.
- the stirrer is not particularly limited, but an inversion stirrer is preferable.
- the reversal rate is 70 to 200 times / minute when phosgene is blown, and 70 to 230 times / minute from the end-stopper addition to the end of the reaction.
- the reaction temperature is preferably 10 to 25 ° C. when phosgene is blown, and 20 to 35 ° C. from the addition of the end terminator to the end of the reaction.
- R 32 , R 33 and R 34 in the general formulas (7a), (8a) and (9a) are respectively an n-octyl group, an iso-octyl group and a t-octyl group. And any one or more of the group consisting of a dodecyl group.
- the polycarbonate resin obtained by the production method according to the present invention has a terminal structure represented by the following general formula (1), and the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less is less than 1% by mass. It has the characteristics. (Wherein R 1 represents a halogen atom, an alkyl group having 5 to 14 carbon atoms, an alkyloxy group having 1 to 23 carbon atoms, or an alkyl ester group having 2 to 23 carbon atoms, and r is an integer of 1 to 5) Represents.)
- the terminal structure represented by the general formula (1) has a structure represented by the following general formula (7), (8) or (9).
- R 33 is an alkyl group having 5 to 14 carbon atoms.
- R 32 is an alkyl group having 1 to 22 carbon atoms.
- R 34 is an alkyl group having 1 to 23 carbon atoms.
- R 32 , R 33 and R 34 in the general formulas (7), (8) and (9) are each composed of an n-octyl group, an iso-octyl group, a t-octyl group and a dodecyl group.
- One or more of the groups are each composed of an n-octyl group, an iso-octyl group, a t-octyl group and a dodecyl group.
- R 6 to R 13 are each independently hydrogen, halogen, an optionally substituted alkoxyl group having 1 to 5 carbon atoms, or an optionally substituted alkyl group having 1 to 20 carbon atoms.
- an alkoxy group having 1 to 5 carbon atoms which may have a substituent an aryl group having 6 to 12 carbon atoms which may have a substituent, and an aryl group having 7 to 17 carbon atoms which may have a substituent
- the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin obtained by the production method according to the present invention is less than 1% by mass.
- the low molecular weight carbonate compound having a molecular weight of 1,000 or less includes, for example, a dicarbonate compound that is a condensation reaction product of a dihydric phenol dichloroformate and a terminal terminator generated by a phosgenation reaction of a dihydric phenol. It is.
- Polycarbonate resins containing a large amount of low molecular weight carbonate compounds with a molecular weight of 1,000 or less are molds (molds) at relatively early stages when injection molding of discs and complicated and thin products is performed continuously. ) Tends to be contaminated by a small amount of deposits (mold deposits). In this respect, if the amount of the low molecular weight carbonate compound having a molecular weight of 1,000 or less is less than 1% by mass, it is preferable because contamination of the mold is effectively prevented.
- the viscosity average molecular weight (Mv) of the polycarbonate resin obtained by the production method of the present invention is preferably 10,000 to 18,000. More preferably, the viscosity average molecular weight (Mv) is from 11,000 to 15,000, and even more preferably, the viscosity average molecular weight (Mv) is from 12,000 to 14,500.
- the viscosity average molecular weight (Mv) is 10,000 or more, the mechanical strength is improved.
- the viscosity average molecular weight (Mv) is 18,000 or less, the melt viscosity is lowered and the fluidity is improved, and it is easy to form a thin-walled / large-sized molded product. become.
- Flow characteristic evaluation device Flow tester Load: 160 kgf / cm 2 Orifice: 1mm diameter x 10mm length Measurement temperature: 240 ° C Measuring instrument: CFT-500D manufactured by Shimadzu Corporation
- ⁇ Mold stain> Using an injection molding machine (“HSP100A” manufactured by Sodick Co., Ltd.), a thin specimen having a resin temperature of 340 ° C. and a mold temperature of 80 ° C. and a thickness of 3.5 inches and a thickness of 0.4 mm was molded and continuously 350 shots molded. Evaluation was made by observing the mold deposit (mold deposit). At that time, the case where it was good without problems was evaluated as “ ⁇ ” (namely, acceptable), and the case where it was soiled and was defective was evaluated as “x” (namely, unacceptable).
- Example 1 7 kg of bisphenol A (BPA) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and 35 g of hydrosulfite were dissolved in 43.5 kg of a 9 w / w% sodium hydroxide aqueous solution. To this, 17.2 kg of dichloromethane was added, and while stirring, 4.1 kg of phosgene was blown in over 30 minutes while maintaining the solution temperature in the range of 15 ° C to 25 ° C.
- BPA bisphenol A
- phosgene phosgene
- the polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing solution became neutral.
- the polycarbonate resin powder was obtained by evaporating the organic solvent from the purified polycarbonate resin solution.
- the obtained polycarbonate resin powder was melt kneaded at a cylinder temperature of 240 ° C. by a single screw extruder with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastic Machinery Co., Ltd.), and pellets were obtained by strand cutting.
- the viscosity average molecular weight was 11,000 and the amount of low molecular weight carbonate compound having a molecular weight of less than 1,000 was 0. 0.85% by mass and Q value was 69 ⁇ 10 ⁇ 2 cc / sec.
- the obtained pellets were dried at 120 ° C. for 4 to 6 hours with a hot-air circulating dryer, and then injected with an injection molding machine (“HSP100A” manufactured by Sodick) at a resin temperature of 340 ° C. and a mold temperature of 80 ° C. for 3.5.
- HSP100A injection molding machine
- a thin specimen having an inch and a thickness of 0.4 mm was continuously formed. The mold stain was good.
- Example 2 A polycarbonate resin pellet and a molded body were obtained in the same manner as in Example 1 except that a solution in which 669 g of the terminal stopper 1 was dissolved in 21.6 kg of dichloromethane (the terminal stopper concentration in the solution: 3%) was used.
- the resulting polycarbonate resin has a viscosity average molecular weight of 12,000, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a mass of 0.94% by mass, and a Q value of 56 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 3 After the completion of the phosgene blowing, a solution (end stopper concentration in the solution: 4%) in which 574 g of the terminal stopper 1 was dissolved in 5 kg of a 9 w / w% aqueous sodium hydroxide solution, 3.4 kg of dichloromethane, and 13.8 kg of dichloromethane.
- a polycarbonate resin pellet and a molded body were obtained in the same manner as in Example 1 except that it was used.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 13,500, a low molecular weight carbonate compound having a molecular weight of less than 1,000, 0.83% by mass, and a Q value of 20 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 4 After the completion of the phosgene blowing, a solution (end stopper concentration in the solution: 6%) obtained by dissolving 574 g of the terminal stopper 1 in 5 kg of a 9 w / w% sodium hydroxide aqueous solution, 11.4 kg of dichloromethane, and 9 kg of dichloromethane was used. Except for the above, polycarbonate resin pellets and molded articles were obtained in the same manner as in Example 1.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 13,500, a low molecular weight carbonate compound having a molecular weight of less than 1,000, 0.93% by mass, and a Q value of 19 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 5 After the completion of the phosgene blowing, a solution in which 487 g of the terminal stopper 1 was dissolved in 5 kg of a 9 w / w% aqueous sodium hydroxide solution, 9 kg of dichloromethane and 7.6 kg of dichloromethane (the concentration of the terminal stopper in the solution: 6%) was used. Except for the above, polycarbonate resin pellets and molded articles were obtained in the same manner as in Example 1.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 14,500, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a mass of 0.62% by mass, and a Q value of 13 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 6 After the completion of the phosgene blowing, a solution in which 396 g of the terminal terminator 1 was dissolved in 5 kg of a 9 w / w% aqueous sodium hydroxide solution, 10.3 kg of dichloromethane and 6.2 kg of dichloromethane (the concentration of the terminal terminator in the solution: 6%) A polycarbonate resin pellet and a molded body were obtained in the same manner as in Example 1 except that it was used.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 16,000, a low molecular weight carbonate compound having a molecular weight of less than 1,000, an amount of 0.58% by mass, and a Q value of 10 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 7 Example 6 except that the end terminator 2 was used instead of the end terminator 1 and a solution obtained by dissolving 693 g of the end terminator 2 in 10.9 kg of dichloromethane (end terminator concentration in the solution: 6%) was used. In the same manner, polycarbonate resin pellets and a molded body were obtained.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 14,500, a low molecular weight carbonate compound having a molecular weight of less than 1,000, 0.09% by mass, a Q value of 38 ⁇ 10 ⁇ 2 cc / sec, It was good.
- Example 8 By using the end terminator 3 instead of the end terminator 1, after completion of the phosgene blowing, 616 g of the end terminator 3 was dissolved in 5 kg of a 9 w / w% aqueous sodium hydroxide solution, 1.9 kg of dichloromethane and 14.8 kg of dichloromethane. A polycarbonate resin pellet and a molded body were obtained in the same manner as in Example 3 except that the above solution (end stopper concentration in the solution: 4%) was used.
- the resulting polycarbonate resin has a viscosity average molecular weight of 14,400, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a content of 0.48% by mass, and a Q value of 34 ⁇ 10 ⁇ 2 cc / sec. It was good.
- Example 9 After the completion of the phosgene blowing, a solution in which 616 g of the terminal stopper 3 was dissolved in 5 kg of a 9 w / w% aqueous sodium hydroxide solution, 7.2 kg of dichloromethane and 9.7 kg of dichloromethane (the concentration of the terminal stopper in the solution: 6%) was obtained. A polycarbonate resin pellet and a molded body were obtained in the same manner as in Example 8 except that it was used.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 14,400, a low molecular weight carbonate compound having a molecular weight of less than 1,000, an amount of 0.56% by mass, and a Q value of 34 ⁇ 10 ⁇ 2 cc / sec. It was good.
- the resulting polycarbonate resin has a viscosity average molecular weight of 9,000, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a content of 2.51% by mass, a Q value of 99 ⁇ 10 ⁇ 2 cc / sec, It was bad.
- the resulting polycarbonate resin has a viscosity average molecular weight of 13,600, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a mass of 1.2% by mass, and a Q value of 18 ⁇ 10 ⁇ 2 cc / sec. It was bad.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 14,500, a low molecular weight carbonate compound having a molecular weight of less than 1,000, 1.23% by mass, and a Q value of 13 ⁇ 10 ⁇ 2 cc / sec. It was bad.
- the resulting polycarbonate resin has a viscosity average molecular weight of 20,000, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a mass of 0.67% by mass, and a Q value of 1 ⁇ 10 ⁇ 2 cc / sec. It was good.
- the polycarbonate resin thus obtained had a viscosity average molecular weight of 11,000, a low molecular weight carbonate compound having a molecular weight of less than 1,000, a quantity of 1.13% by mass, and a Q value of 62 ⁇ 10 ⁇ 2 cc / sec. It was bad.
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Abstract
Description
[1]下記一般式(1)に示す末端構造を有し、かつ、粘度平均分子量が10,000~18,000であるポリカーボネート樹脂であって、
該ポリカーボネート樹脂中に含まれる、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満である、ポリカーボネート樹脂。
R1は、ハロゲン原子、炭素数5~14のアルキル基、炭素数1~23のアルキルオキシ基、又は炭素数2~23のアルキルエステル基を表し、
rは1~5の整数を表す。)
[2]前記ポリカーボネート樹指が、下記一般式(2)で表される構造単位を含有するものである、[1]に記載のポリカーボネート樹脂。
R6~R13はそれぞれ独立に、水素、ハロゲン、置換基を有してもよい炭素数1~5のアルコキシル基、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数7~17のアラルキル基及び置換基を有してもよい炭素数2~15のアルケニル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
Xは、単結合、-O-、-S-、-SO-、-SO2-、-CO-及び下記一般式(3)~(6)からなる群のうち、いずれかの構造を表す。)
R14及びR15はそれぞれ独立に水素、ハロゲン、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数2~5のアルケニル基、及び置換基を有してもよい炭素数7~17のアラルキル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
cは1~20の整数を表す。)
(式中、R16及びR17はそれぞれ独立に水素、ハロゲン、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数2~5のアルケニル基及び置換基を有してもよい炭素数7~17のアラルキル基からなる群のうちいずれかを表すか、又は、R16及びR17はそれぞれ互いに結合して、炭素数1~20の炭素環若しくは複素環を形成し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
[3]前記一般式(2)におけるXが、前記一般式(3)に示す構造を有する、[1]または[2]に記載のポリカーボネート樹脂。
[4]前記一般式(2)で表される構造単位が、2,2-ビス(4-ヒドロキシフェニル)プロパンから誘導される構造単位である、[1]~[3]のいずれかに記載のポリカーボネート樹脂。
[5]前記一般式(1)で表される末端構造が、下記一般式(7)、(8)又は(9)で示される構造を有する、[1]~[4]のいずれかに記載のポリカーボネート樹脂。
[6]前記一般式(7)におけるR33が、n-オクチル基、イソ-オクチル基、t-オクチル基及びドデシル基からなる群のうち、いずれか一種以上である、[5]に記載のポリカーボネート樹脂。
[7]2価フェノールと下記一般式(1a)で表される末端停止剤とを用いて界面重合反応によってポリカーボネート樹脂を製造する方法であって、
R1は、ハロゲン原子、炭素数5~14のアルキル基、炭素数1~23のアルキルオキシ基、又は炭素数2~23のアルキルエステル基を表し、
rは1~5の整数を表す。)
前記界面重合反応において、
前記2価フェノールを含む溶液に前記末端停止剤を10質量%未満の濃度で含む末端停止剤溶液を添加する工程を含む、ポリカーボネート樹脂を製造する方法。
[8]前記末端停止剤溶液を添加する工程の前に、前記2価フェノールを含む溶液にホスゲンを吹き込む工程を含む、[7]に記載の方法。
[9]前記末端停止剤溶液が、メチレンクロライド、テトラクロロエタン、クロロホルム、1,2-ジクロルエチレン、トリクロロエタン、ジクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエン、アセトフェノン、シクロヘキサンおよびアニソールからなる群から選択される溶媒を含む、[7]または[8]に記載の方法。
[10]前記末端停止剤溶液が、メチレンクロライドを含む、[7]~[9]のいずれかに記載の方法。
[11]前記2価フェノールが、下記一般式(2a)で表される化合物である、[7]~[10]のいずれかに記載の方法。
R6~R13はそれぞれ独立に、水素、ハロゲン、置換基を有してもよい炭素数1~5のアルコキシル基、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数7~17のアラルキル基及び置換基を有してもよい炭素数2~15のアルケニル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
Xは、単結合、-O-、-S-、-SO-、-SO2-、-CO-及び下記一般式(3)~(6)からなる群のうち、いずれかの構造を表す。)
R14及びR15はそれぞれ独立に水素、ハロゲン、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数2~5のアルケニル基、及び置換基を有してもよい炭素数7~17のアラルキル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
cは1~20の整数を表す。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
[12]前記一般式(2a)におけるXが、前記一般式(3)に示す構造を有する、[11]に記載の方法。
[13]前記一般式(2a)で表される化合物が、2,2-ビス(4-ヒドロキシフェニル)プロパンである、[11]または[12]に記載の方法。
[14]前記末端停止剤が、下記一般式(7a)、(8a)又は(9a)で示される化合物である、[7]~[13]のいずれか一項に記載の方法。
[15]前記末端停止剤が、前記一般式(7a)で示される化合物である、[14]に記載の方法。
[16]前記一般式(7a)におけるR33が、n-オクチル基、イソ-オクチル基、t-オクチル基及びドデシル基からなる群のうち、いずれか一種以上である、[15]に記載の方法。
[17]前記ポリカーボネート樹脂の粘度平均分子量が10,000~18,000である、[7]~[16]のいずれかに記載の方法。
[18]前記ポリカーボネート樹脂中に含まれる、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満である、[7]~[17]のいずれかに記載の方法。
第1の態様は、例えば以下の発明を含む。
下記一般式(1)に示す末端構造を有し、かつ、粘度平均分子量が10,000~18,000であるポリカーボネート樹脂であって、
該ポリカーボネート樹脂中に含まれる、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満である、ポリカーボネート樹脂。
R1は、ハロゲン原子、炭素数5~14のアルキル基、炭素数1~23のアルキルオキシ基、又は炭素数2~23のアルキルエステル基を表し、
rは1~5の整数を表す。)
〔ポリカーボネート樹脂〕
本発明によるポリカーボネート樹脂は、下記一般式(1)で表される末端構造を有し、かつ、粘度平均分子量が10,000~18,000である。さらに、ポリカーボネート樹脂中に含まれる、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満であるという特徴を有する。
cは1~20の整数を表す。)
本発明のポリカーボネート樹脂を製造するのに用いられる2価フェノールは、分子中に二つの水酸基を有するフェノール系化合物であれば特に限定されないが、得られる成形体の耐衝撃性と、純度が高く、流通量が多いという観点から下記一般式(2a)で表される2価フェノールが好ましい。このような2価フェノールを用いることで、得られるポリカーボネート樹脂が一般式(2)で表される構造単位を有することとなる。
本発明のポリカーボネート樹脂の製造に用いる炭酸エステル形成化合物は、ホスゲン、トリホスゲン、炭酸ジエステル、及び、カルボニル化合物が例示される。炭酸エステル形成化合物の中でも、特にホスゲンが、得られる樹脂の色相や安定性などの品質、更にはコストの観点から好ましい。
さらに、パラ-t-オクチルフェノール、パラヒドロキシ安息香酸2-エチルヘキシルエステル、パラ-n-オクチルオキシフェノールのいずれかもしくは複数を末端停止剤として使用することが、流動性、成形体の強度および耐熱性に加え、入手のし易さの観点からより好ましい。
他の末端停止剤を使用する場合は、全末端停止剤中の20mol%以下であることが好ましく、10mol%以下であることがより好ましい。
本発明のポリカーボネート樹脂は、末端停止剤の使用量によって分子量が制御される。 主骨格のために使用する2価フェノールの重合度と、末端停止剤の使用量は下記数式(I)に示される。
本発明のポリカーボネート樹脂には、必要に応じて、他の樹脂が含まれていてもよい。このような他の樹脂としては、例えば、本発明で用いるポリカーボネート樹脂以外のポリカーボネート樹脂、ポリエチレンテレフタレート樹脂(PET樹脂)、ポリトリメチレンテレフタレート(PTT樹脂)、ポリブチレンテレフタレート樹脂(PBT樹脂)等の熱可塑性ポリエステル樹脂;ポリスチレン樹脂(PS樹脂)、高衝撃ポリスチレン樹脂(HIPS)、アクリロニトリル-スチレン共重合体(AS樹脂)、メチルメタクリレート-スチレン共重合体(MS樹脂)等のスチレン系樹脂;メチルメタクリレート-アクリルゴム-スチレン共重合体(MAS)等のコア/シェル型のエラストマー、ポリエステル系エラストマー等のエラストマー;環状シクロオレフィン樹脂(COP樹脂)、環状シクロオレフィン(COP)共重合体樹脂等のポリオレフィン樹脂;ポリアミド樹脂(PA樹脂);ポリイミド樹脂(PI樹脂);ポリエーテルイミド樹脂(PEI樹脂);ポリウレタン樹脂(PU樹脂);ポリフェニレンエーテル樹脂(PPE樹脂);ポリフェニレンサルファイド樹脂(PPS樹脂);ポリスルホン樹脂(PSU樹脂);ポリメタクリレート樹脂(PMMA樹脂);ポリカプロラクトン等を挙げることができる。特に好ましい混合樹脂としては、PS樹脂、AS樹脂、PMMA樹脂が挙げられる。
本発明のポリカーボネート樹脂中における、他の樹脂の成分割合は、全樹脂成分の10質量%以下であることが好ましく、1質量%以下がさらに好ましい。他の樹脂の成分割合を10質量%以下とすることで、諸物性を維持することができる。
本発明のポリカーボネート樹脂には、本発明の主旨を逸脱しない範囲で種々の添加剤が配合されていてもよい。添加剤としては、熱安定剤、酸化防止剤、難燃剤、難燃助剤、紫外線吸収剤、離型剤及び着色剤から成る群から選択された少なくとも1種類の添加剤が例示される。
また、所望の諸物性を著しく損なわない限り、帯電防止剤、蛍光増白剤、防曇剤、流動性改良剤、可塑剤、分散剤、抗菌剤等を添加してもよい。
また、フルオロアルカン-スルホン酸金属塩として、アルカリ金属塩およびアルカリ土類金属塩を挙げることができ、その中でもアルカリ金属塩が好ましい。フルオロアルカンスルホン酸金属塩の炭素数としては、1~8が好ましく、2~4がより好ましい。このような範囲とすることにより、高い透明性を維持できるという効果が得られる。好ましいフルオロアルカン-スルホン酸金属塩の具体例として、パーフルオロブタン-スルホン酸ナトリウム、パーフルオロブタン-スルホン酸カリウム、パーフルオロエタン-スルホン酸ナトリウム、パーフルオロエタン-スルホン酸カリウム、等を挙げることができる。
離型剤の添加割合は、配合する場合、ポリカーボネート樹脂100質量部に対して、好ましくは0.001質量部以上、より好ましくは0.01質量部以上であり、また、2質量部以下、より好ましくは1質量部以下である。離型剤の添加割合が少なすぎると、成形時の離型性の効果が十分でない場合があり、離型剤の添加割合が多すぎると、成形体の耐加水分解性の低下、射出成形時の金型汚染等が生じる可能性がある。
着色剤の添加割合は、配合する場合、ポリカーボネート樹脂100質量部に対して、例えば5質量部以下、好ましくは3質量部以下、より好ましくは2質量部以下である。着色剤の添加割合が多すぎると成形体の耐衝撃性が十分で無くなる可能性がある。
本発明のポリカーボネート樹脂は、公知の方法に基づき合成することができるが、追加の精製工程を用いずに分子量が1,000以下の低分子量カーボネート化合物の量を1質量%未満に抑える観点から、界面重合法によって合成するのが好ましい。あるいは、本発明のポリカーボネート樹脂は、本発明の第2の態様に記載の方法で合成してもよい。第2の態様については、本明細書において後述する。
<分子量>
本発明の成形体に含まれるポリカーボネート樹脂の分子量はウベローデ粘度計を用い、以下に示す条件にて測定した粘度平均分子量(Mv)にて評価する。
測定機器:ウベローデ毛管粘度計
溶媒:ジクロロメタン
樹脂溶液濃度:0.5グラム/デシリットル
測定温度:25℃
上記条件で測定し、ハギンズ定数0.45で極限粘度[η]デシリットル/グラムを求め、下記数式(II)により算出する。
本発明のポリカーボネート樹脂に含まれる分子量が1,000以下の低分子量カーボネート化合物の量は、以下に示す条件にて行うゲル浸透クロマトグラフ分析にて評価する。
測定機種:東ソー社製 HLC-8320GPC
カラム:Shodex K-G+K-805Lx2本+K-800D
溶離液:クロロホルム
温度:カラム恒温槽40℃
流速:1.0 ml/min
濃度:0.lwt/vol%
注入量:100μl
前処理:0.45μmフィルターでろ過
検出器:示差屈折計(RI)
上記条件で測定し、試料のポリスチレン換算分子量分布を求め、その結果から分子量1,000未満の低分子量カーボネート化合物の量[質量%]を算出することができる。
本発明のポリカーボネート樹脂の溶融流動性は高化式フローテスターを用い、以下に示す条件にて測定した容量流速(Q値)にて評価する。Q値が高いと溶融流動性が高いことを示し、Q値が低いと溶融流動性が低いことを示す。
測定機器:高化式フローテスター
荷重:160kgf/cm2
オリフィス:直径1mm×長さ10mm
測定温度:240℃
試験には例えば、株式会社島津製作所製CFT-500Dを使用することができる。
射出成形機(ソディック社製「HSP100A」)により、樹脂温度340℃、金型温度80℃で3.5インチ、厚み0.4mmの薄肉試験片を成形し連続350ショット成形した後、成形後の金型付着物を観察することで評価することができる。
本発明のポリカーボネート樹脂は、従来のポリカーボネート樹脂に比べて、流動性が高く、さらにモールドデポジットなどの金型汚れを低減することができることから、自動車用照明装置に内蔵される導光部材、液晶バックライトユニットや各種の表示装置、照明装置の分野の導光板用に適している。このような導光板を用いる装置の例としては、携帯電話、モバイルノート、ネットブック、スレートPC、タブレットPC、スマートフォン、タブレット型端末等の携帯端末、カメラ、時計、ノートパソコン、各種ディスプレイ、照明機器等が挙げられる。本発明の一態様によれば、本発明のポリカーボネート樹脂を含む導光板が提供される。
第2の態様は、例えば以下の発明を含む。
2価フェノールと下記一般式(1a)で表される末端停止剤とを用いて界面重合反応によってポリカーボネート樹脂を製造する方法であって、
R1は、ハロゲン原子、炭素数5~14のアルキル基、炭素数1~23のアルキルオキシ基、又は炭素数2~23のアルキルエステル基を表し、
rは1~5の整数を表す。)
前記界面重合反応において、
前記2価フェノールを含む溶液に前記末端停止剤を10質量%未満の濃度で含む末端停止剤溶液を添加する工程を含む、ポリカーボネート樹脂を製造する方法。
<ポリカーボネート樹脂の製造方法>
本発明の1つの実施形態によると、2価フェノールと下記一般式(1a)で表される末端停止剤とを用いて界面重合反応によってポリカーボネート樹脂を製造する方法であって、
界面重合反応において、2価フェノールを含む溶液に末端停止剤を10質量%未満の濃度で含む末端停止剤溶液を添加する工程を含む、ポリカーボネート樹脂を製造する方法が提供される。
本発明の製造方法に用いられる2価フェノール及び炭酸エステル形成化合物は、第1の態様において記載したものと同様であるため、記載を省略する。
本発明の製造方法に用いられる末端停止剤についても、第1の態様において記載したものと同様であるため、記載を省略する。なお、本発明の製造方法の好ましい態様において、一般式(7a)、(8a)および(9a)におけるR32、R33およびR34はそれぞれn-オクチル基、イソ-オクチル基、t-オクチル基及びドデシル基からなる群のうち、いずれか一種以上である。
本発明の製造方法に用いられる末端停止剤(1価フェノール)の使用量は、第1の態様において記載したものと同様であるため、記載を省略する。
本発明の製造方法によって得られるポリカーボネート樹脂に必要に応じて混合できる他の樹脂は、第1の態様において記載したものと同様であるため、記載を省略する。
本発明の製造方法によって得られるポリカーボネート樹脂に、本発明の主旨を逸脱しない範囲で配合可能な種々の添加剤は、第1の態様において記載したものと同様であるため、記載を省略する。
本発明による製造方法によって得られるポリカーボネート樹脂は、下記一般式(1)で表される末端構造を有し、かつ、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満であるという特徴を有する。
本発明の製造方法によって得られるポリカーボネート樹脂の種々の物性に関する評価方法は、第1の態様において記載したものと同様であるため、記載を省略する。
本発明の製造方法によって得られるポリカーボネート樹脂の用途は、第1の態様において記載したものと同様であるため、記載を省略する。
本実施例において得られた成形体に含まれるポリカーボネート樹脂の分子量は、ウベローデ粘度計を用い、以下に示す条件にて測定した粘度平均分子量(Mv)にて評価した。
測定機器:ウベローデ毛管粘度計
溶媒:ジクロロメタン
樹脂溶液濃度:0.5グラム/デシリットル
測定温度:25℃
上記条件で測定し、ハギンズ定数0.45で極限粘度[η]デシリットル/グラムを求め、下記数式(II)により算出した。
測定機種:東ソー社製 HLC-8320GPC
カラム:Shodex K-G+K-805Lx2本+K-800D
溶離液:クロロホルム
温度:カラム恒温槽40℃
流速:1.0 ml/min
濃度:0.lwt/vol%
注入量:100μl
前処理:0.45μmフィルターでろ過
検出器:示差屈折計(RI)
上記条件で測定し、試料のポリスチレン換算分子量分布を求め、その結果から分子量1,000未満の低分子量カーボネート化合物の量[質量%]を算出した。
測定機器:流動特性評価装置フローテスター
荷重:160kgf/cm2
オリフィス:直径1mm×長さ10mm
測定温度:240℃
測定機器:株式会社島津製作所製CFT-500D
射出成形機(ソディック社製「HSP100A」)により、樹脂温度340℃、金型温度80℃で3.5インチ、厚み0.4mmの薄肉試験片を成形し連続350ショット成形した後、成形後の金型付着物(モールドデポジット)を観察することで評価した。その際、問題なく良好であった場合を「○」(すなわち、合格)とし、汚れが発生し不良だった場合を「×」(すなわち、不合格)と評価した。
<製造例1>
有機化学ハンドブック(第3版:有機合成化学協会編:技術堂発行)の第210頁~212頁の記載に基づき、東京化成工業株式会社製のフェノールと東京化成工業株式会社製の2,4,4-トリメチル-1-ペンテンを用いてアルキル化を行い、下記化学式のパラ-t-オクチルフェノール(末端停止剤1)を得た。
有機化学ハンドブック(第3版:有機合成化学協会編:技術堂発行)の第143頁~150頁の記載に基づき、東京化成工業株式会社製の4-ヒドロキシ安息香酸と三菱化学株式会社製の2-エチルヘキサノールを用いて脱水反応によるエステル化を行い、下記化学式のパラヒドロキシ安息香酸2-エチルヘキシルエステル(末端停止剤2)を得た。
有機化学ハンドブック(第3版:有機合成化学協会編:技術堂発行)の第138頁~140頁の記載に基づき、東京化成工業株式会社製のヒドロキノンと東京化成工業株式会社製のオクタノールを用いてエーテル化を行い、下記化学式のパラ-n-オクチルオキシフェノール(末端停止剤3)を得た。
<実施例1>
9w/w%の水酸化ナトリウム水溶液43.5kgに、新日鉄住金化学株式会社製のビスフェノールA(BPA)7kgとハイドロサルファイト35gを加えて溶解した。これにジクロロメタン17.2kgを加え、撹拌しながら、溶液温度を15℃~25℃の範囲に保ちつつ、ホスゲン4.1kgを30分かけて吹き込んだ。
ジクロロメタン21.6kgに末端停止剤1を669g溶解させた溶液(溶液中の末端停止剤濃度:3%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン3.4kg及びジクロロメタン13.8kgに末端停止剤1を574g溶解させた溶液(溶液中の末端停止剤濃度:4%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン11.4kg及びジクロロメタン9kgに末端停止剤1を574g溶解させた溶液(溶液中の末端停止剤濃度:6%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン9kg及びジクロロメタン7.6kgに末端停止剤1を487g溶解させた溶液(溶液中の末端停止剤濃度:6%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン10.3kg及びジクロロメタン6.2kgに末端停止剤1を396g溶解させた溶液(溶液中の末端停止剤濃度:6%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
末端停止剤1の代わりに末端停止剤2を用いて、ジクロロメタン10.9kgに末端停止剤2を693g溶解させた溶液(溶液中の末端停止剤濃度:6%)を用いた以外は実施例6と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
末端停止剤1の代わりに末端停止剤3を用いて、ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン1.9kg及びジクロロメタン14.8kgに末端停止剤3を616g溶解させた溶液(溶液中の末端停止剤濃度:4%)を用いた以外は実施例3と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン7.2kg及びジクロロメタン9.7kgに末端停止剤3を616g溶解させた溶液(溶液中の末端停止剤濃度:6%)を用いた以外は、実施例8と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン8.4kg及びジクロロメタン8.1kgに末端停止剤1を910g溶解させた溶液(溶液中の末端停止剤濃度:10%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ジクロロメタン5.1kgに末端停止剤1を574g溶解させた溶液(溶液中の末端停止剤濃度:10%)を用いた以外は、実施例4と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン13.8kg及びジクロロメタン2.8kgに末端停止剤1を487g溶解させた溶液(溶液中の末端停止剤濃度:15%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
ホスゲンの吹き込み終了後、9w/w%の水酸化ナトリウム水溶液5kg、ジクロロメタン14.2kg及びジクロロメタン2.3kgに末端停止剤1を264g溶解させた溶液(溶液中の末端停止剤濃度:10%)を用いた以外は、実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
末端停止剤1の代わりに末端停止剤4(東京化成工業株式会社製のパラ-t-ブチルフェノール)を用いて、ジクロロメタン51.6kgに末端停止剤4を522g溶解させた溶液(溶液中の末端停止剤濃度:1%)を用いた以外は実施例1と同様にしてポリカーボネート樹脂ペレット及び成形体を得た。
Claims (18)
- 前記ポリカーボネート樹指が、下記一般式(2)で表される構造単位を含有するものである、請求項1に記載のポリカーボネート樹脂。
R6~R13はそれぞれ独立に、水素、ハロゲン、置換基を有してもよい炭素数1~5のアルコキシル基、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数7~17のアラルキル基及び置換基を有してもよい炭素数2~15のアルケニル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
Xは、単結合、-O-、-S-、-SO-、-SO2-、-CO-及び下記一般式(3)~(6)からなる群のうち、いずれかの構造を表す。)
R14及びR15はそれぞれ独立に水素、ハロゲン、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数2~5のアルケニル基、及び置換基を有してもよい炭素数7~17のアラルキル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
cは1~20の整数を表す。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
- 前記一般式(2)におけるXが、前記一般式(3)に示す構造を有する、請求項1または2に記載のポリカーボネート樹脂。
- 前記一般式(2)で表される構造単位が、2,2-ビス(4-ヒドロキシフェニル)プロパンから誘導される構造単位である、請求項1~3のいずれか一項に記載のポリカーボネート樹脂。
- 前記一般式(7)におけるR33が、n-オクチル基、イソ-オクチル基、t-オクチル基及びドデシル基からなる群のうち、いずれか一種以上である、請求項5に記載のポリカーボネート樹脂。
- 前記末端停止剤溶液を添加する工程の前に、前記2価フェノールを含む溶液にホスゲンを吹き込む工程を含む、請求項7に記載の方法。
- 前記末端停止剤溶液が、メチレンクロライド、テトラクロロエタン、クロロホルム、1,2-ジクロルエチレン、トリクロロエタン、ジクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエン、アセトフェノン、シクロヘキサンおよびアニソールからなる群から選択される溶媒を含む、請求項7または8に記載の方法。
- 前記末端停止剤溶液が、メチレンクロライドを含む、請求項7~9のいずれか一項に記載の方法。
- 前記2価フェノールが、下記一般式(2a)で表される化合物である、請求項7~10のいずれか一項に記載の方法。
R6~R13はそれぞれ独立に、水素、ハロゲン、置換基を有してもよい炭素数1~5のアルコキシル基、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数7~17のアラルキル基及び置換基を有してもよい炭素数2~15のアルケニル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
Xは、単結合、-O-、-S-、-SO-、-SO2-、-CO-及び下記一般式(3)~(6)からなる群のうち、いずれかの構造を表す。)
R14及びR15はそれぞれ独立に水素、ハロゲン、置換基を有してもよい炭素数1~20のアルキル基、置換基を有してもよい炭素数1~5のアルコキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数2~5のアルケニル基、及び置換基を有してもよい炭素数7~17のアラルキル基からなる群のうちいずれかを表し、
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基であり、
cは1~20の整数を表す。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
前記置換基はそれぞれ独立に、ハロゲン、炭素数1~20のアルキル基、又は炭素数6~12のアリール基である。)
- 前記一般式(2a)におけるXが、前記一般式(3)に示す構造を有する、請求項11に記載の方法。
- 前記一般式(2a)で表される化合物が、2,2-ビス(4-ヒドロキシフェニル)プロパンである、請求項11または12に記載の方法。
- 前記末端停止剤が、前記一般式(7a)で示される化合物である、請求項14に記載の方法。
- 前記一般式(7a)におけるR33が、n-オクチル基、イソ-オクチル基、t-オクチル基及びドデシル基からなる群のうち、いずれか一種以上である、請求項15に記載の方法。
- 前記ポリカーボネート樹脂の粘度平均分子量が10,000~18,000である、請求項7~16のいずれか一項に記載の方法。
- 前記ポリカーボネート樹脂中に含まれる、分子量が1,000以下の低分子量カーボネート化合物の量が1質量%未満である、請求項7~17のいずれか一項に記載の方法。
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