Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • 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
  • C08G64/1691—Aliphatic-aromatic or araliphatic polycarbonates unsaturated
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
  • C08K5/25—Carboxylic acid hydrazides
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/372—Sulfides, e.g. R-(S)x-R'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

• the present invention relates to a polycarbonate resin composition.
• Aliphatic polycarbonates have been known to be useful as medical materials and engineering plastics because of their excellent properties such as impact resistance and light weight. have.
• alicyclic polycarbonates having an alicyclic structure in their main chain structure exhibit a higher glass transition point than other aliphatic polycarbonates, and are being actively developed.
• a polycyclic alicyclic polycarbonate resin having pentacyclopentadecanedimethanol as a skeleton and excellent transparency, heat resistance and color tone is disclosed (see, for example, Patent Document 1).
• a polycarbonate resin using isosorbide as a raw material which uses not only petroleum raw materials but also biomass-derived raw materials and has an excellent balance of transparency, heat resistance, water absorption, surface hardness, low birefringence, etc. (For example, see Patent Document 2)
• poly(1,2-cyclohexene carbonate) having a cyclohexane skeleton is the simplest alicyclic polycarbonate having saturated carbon six-membered rings corresponding to benzene rings. It is widely known that poly(1,2-cyclohexene carbonate) can be synthesized by copolymerization of cyclohexene oxide and carbon dioxide, ring-opening polymerization of 1,2-cyclohexene carbonate (for example, Patent Document 3 and non- See Patent Document 1).
• the poly(1,2-cyclohexene carbonate) obtained as described above has transparency and the property of being completely decomposed at a predetermined temperature, and is expected to be used in optical materials, thermal decomposition materials, etc. there is
• poly(1,2-cyclohexene carbonate) has excellent transparency, it may be thermally decomposed during the molding process, and the associated decrease in mechanical strength may occur, so there is room for improvement.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin composition having excellent thermal stability.
• one or more selected from the group consisting of a compound having an amide bond, a sulfur compound, and a phosphite ester compound is used.
• the inventors have found that the thermal stability of the polycarbonate resin composition is remarkably improved, leading to the present invention.
• the present invention is as follows.
• a polycarbonate resin comprising a structural unit having an alicyclic hydrocarbon moiety in which a carbonate group is linked to two adjacent carbon atoms forming a ring; one or more selected from the group consisting of compounds having an amide bond, sulfur compounds, and phosphite ester compounds,
• the polycarbonate resin composition wherein the polycarbonate resin has a weight average molecular weight Mw of 50,000 or more and 500,000 or less as measured by size exclusion chromatography using polystyrene as a standard sample.
• the polycarbonate resin composition according to [1], wherein the structural unit having the alicyclic hydrocarbon moiety is represented by the following formula (1).
• n represents an integer of 1 to 6
• R 1 to R 6 each independently represent a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, a vinyl group, an allyl group, a an alkoxy group of ⁇ 20, an ester group of 1 to 20 carbon atoms, an acyl group of 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms, an alkylene group or may be bonded to each other through a carbonate group to form a cyclic structure, the alkylene group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group; A carbonyl group may be inserted, and the alkoxy group, the ester group, the acyl group, and the alkyl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms.
• the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group.
• R 13 is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms.
• R 11 and R 12 are each independent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, the alkylene group, the alkenylene group, the alkoxylylene group, the alkyl group, the alkenyl group, the alkoxy group, and the cycloalkyl groups, said aralkyl groups, said aryl groups and said heteroaryl groups may be substituted with hydroxyl groups, phosphoric acid groups, amino groups, alkoxy groups or ester groups, said aralkyl groups, said aryl groups and said The heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atom
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms.
• the aryl group and the heteroaryl group may be substituted with an alkyl group having 1 to 6 carbon atoms, and the aralkyl group, the aryl group and the heteroaryl group each have a carbon number It may be substituted with 1 to 20 alkyl groups.
• the content of the sulfur compound is 500 mass ppm to 10000 mass ppm, [1] The polycarbonate resin composition according to any one of [9].
• the sulfur compound has a structure represented by the following formula (2-1), [1] The polycarbonate resin composition according to any one of [10].
• R 13 and R 14 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms.
• R 11 and R 12 each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or a cycloalkyl group having 7 to 20 carbon atoms.
• the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group.
• the sulfur compound has a structure represented by the following formula (3-1), [1] The polycarbonate resin composition according to any one of [10].
• m represents an integer of 1 to 4
• each R 12 is independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or 1 carbon atom to 20 alkoxylene groups
• each R 11 is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a carbon an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms
• R 13 is an m-valent hydrocarbon group optionally having an alkoxy group and
• [13] Containing the compound having the amide bond and the sulfur compound, [1] The polycarbonate resin composition according to any one of [12]. [14] The content of the compound having an amide bond and the content of the sulfur compound are each 500 ppm by mass to 10000 ppm by mass, [1] The polycarbonate resin composition according to any one of [13]. [15] The content of the phosphite compound is 500 mass ppm to 10000 mass ppm, [1] The polycarbonate resin composition according to any one of [14]. [16] The phosphite compound has a structure represented by the following formula (2-2), [1] The polycarbonate resin composition according to any one of [15].
• m represents an integer of 0 to 3
• R 11 to R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.
• the phosphite ester compound has a structure represented by the following formula (3-2), [1] The polycarbonate resin composition according to any one of [15].
• m represents an integer of 1 to 4;
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.
• R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or 7 to 20 carbon atoms.
• R 15 is an m-valent hydrocarbon group, the alkyl group, the alkenyl group, the alkoxy group , the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group; group and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.) [18] containing the compound having an amide bond and a phosphite ester compound, [1] The polycarbonate resin composition according to any one of [17]. [19] The content of the compound having an amide bond and the phosphite ester compound is Each is 500 mass ppm to 10000 mass ppm, [1] The polycarbonate resin composition
• an alicyclic polycarbonate resin composition having excellent thermal stability can be provided.
• this embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents.
• the present invention can be carried out with various modifications within the scope of its gist.
• the polycarbonate resin composition of the present embodiment comprises a polycarbonate resin containing a structural unit having an alicyclic hydrocarbon moiety in which a carbonate group is linked to two adjacent carbon atoms forming a ring, a compound having an amide bond, and a sulfur compound. , And one or more selected from the group consisting of phosphite ester compounds, and the weight average molecular weight Mw measured by size exclusion chromatography using polystyrene as a standard sample in the polycarbonate resin is 50,000 or more and 500,000 or less.
• the polycarbonate resin composition of the present embodiment has excellent thermal stability due to the characteristics described above.
• the thermal decomposition mechanism of the polycarbonate resin used in the present embodiment has not been clarified, it is thought to be due to elimination of the monomer due to a ring closure reaction of the carbonate group at the terminal of the polymer.
• the alicyclic hydrocarbon has an alicyclic hydrocarbon moiety in which a carbonate group is linked to two adjacent carbons
• the above ring closure reaction proceeds easily, but the polycarbonate resin has an amide bond, a sulfur compound , and a phosphite ester compound, by adding one or more selected from the group consisting of a phosphite ester compound, a hydrogen bonding action occurs between the carbonate group at the end of the polymer and the added compound, and the ring closure reaction of the carbonate group occurs.
• the above mechanism is speculative and non-limiting.
• polycarbonate resin used in the polycarbonate resin composition of the present embodiment is a structural unit having an alicyclic hydrocarbon moiety in which a carbonate group is linked to two adjacent carbon atoms forming a ring (hereinafter simply referred to as "alicyclic hydrocarbon (also referred to as "a structural unit having a site”).
• alicyclic hydrocarbon also referred to as "a structural unit having a site”
• a structural unit having an alicyclic hydrocarbon moiety is preferably represented by the following formula (1).
• n represents an integer of 1 to 6
• R 1 to R 6 each independently represent a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, a vinyl group, an allyl group, a ⁇ 20 alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), ester group of 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 11 carbon atoms) , an acyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 11 carbon atoms), or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms (preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), may be bonded to each other through an alkylene group or a carbonate group to form a cyclic structure, the alkylene group is a hydroxyl group, a phosphoric acid group, an amino group,
• a phosphate group, an amino group, an alkoxy group, or an ester group, and the aralkyl group, the aryl group, and the heteroaryl group are substituted with an alkyl group having 1 to 20 carbon atoms.
• n 1, it means that the ring structure is cyclopentane; when n is 2, it means that the ring structure is cyclohexane; When n is 4, it means that the ring structure is cyclooctane; when n is 5, it means that the ring structure is cyclononane; means that the ring structure is cyclodecane.
• the two wavy line portions are the connecting portions of the repeating units.
• n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, from the viewpoint of availability of raw materials.
• R 4 to R 6 may be hydrogen atoms.
• the polycarbonate resin used in the present embodiment preferably contains a structural unit represented by the following formula (5) having terminal structures represented by A 1 and A 2 .
• a 1 and A 2 each independently represent a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, a vinyl group, an allyl group, a phenyl group, a benzyl group, or an alkoxy group having 1 to 10 carbon atoms.
• n and R 1 to R 6 are the same as in formula (1).
• the number of repetitions of the structural unit represented by formula (5) is, for example, 300-3500.
• R 4 to R 6 may be hydrogen atoms.
• the polycarbonate resin used in this embodiment is preferably poly(1,2-cyclohexene carbonate).
• the polycarbonate resin composition of the present embodiment when the polycarbonate resin is poly(1,2-cyclohexene carbonate), it tends to be excellent in heat stability and transparency.
• the polycarbonate resin used in the present embodiment has a weight average molecular weight Mw of 50,000 or more and 500,000 or less as measured by size exclusion chromatography using polystyrene as a standard sample.
• the polycarbonate resin of the present embodiment has an Mw within the above range, so that molding processing is facilitated.
• Mw is more preferably 80,000 or more and 400,000 or less, and still more preferably 100,000 or more and 300,0000 or less.
• the polycarbonate resin used in the present embodiment has a number average molecular weight Mn measured by size exclusion chromatography using polystyrene as a standard sample, preferably 50,000 or more and 500,000 or less, more preferably 80,000 or more. It is 400,000 or less, more preferably 100,000 or more and 300,0000 or less.
• the weight average molecular weight and number average molecular weight of the polycarbonate resin by size exclusion chromatography can be specifically measured by the method described in Examples.
• the ratio of the polymerizable monomer and the polymerization initiator and additives may be adjusted as appropriate.
• the polycarbonate resin may be produced by the production method described later.
• Mw and Mn tend to be increased by reducing the ratio of the polymerization initiator to the polymerizable monomer. Furthermore, there is a tendency that Mw and Mn can be increased by stirring using a stirring blade and a flow mixer.
• the glass transition temperature Tg of the polycarbonate resin used in the present embodiment measured by a differential scanning calorimeter is preferably 80° C. or higher and 180° C. or lower, more preferably 90° C. or higher and 180° C. or lower, and 100° C. More preferably, the temperature is at least 180°C.
• the thermal stability tends to be more excellent.
• the method for controlling the glass transition temperature Tg of the polycarbonate resin within the above range is not particularly limited, but examples include a method for controlling the weight average molecular weight and number average molecular weight of the polycarbonate resin.
• the molecular arrangement of the polycarbonate resin used in the present embodiment includes random copolymers, alternating copolymers, and block copolymers. It may have the above polymerization sequences.
• the stereoregularity of the polycarbonate resin used in the present embodiment includes an isotactic structure, a syndiotactic structure, and an atactic structure. From the viewpoint of further improving transparency, an atactic structure that becomes amorphous is preferable.
• the method for producing the polycarbonate resin used in the present embodiment is not particularly limited.
• ring-opening polymerization of an alicyclic cyclic carbonate represented by the following formula (6) alicyclic Examples thereof include conventional methods such as copolymerization of a cyclic oxide with carbon dioxide and transesterification between an alicyclic diol represented by the following formula (8) and a carbonate precursor.
• R 1 to R 6 each independently represent a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, a vinyl group, an allyl group, , an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), an ester group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 11), an acyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 11 carbon atoms), or a linear, branched or cyclic C 1 to 20 an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), which may be bonded to each other via an alkylene group or a carbonate group to form a cyclic structure, and the alkylene group is may be
• Ring-opening polymerization In the method for producing a polycarbonate resin used in the present embodiment, as the cyclic carbonate used for ring-opening polymerization, one type of alicyclic cyclic carbonate may be used alone, and R 1 to R 6 in formula (6) are Any two or more different alicyclic cyclic carbonates may be used in combination.
• the initiator for ring-opening polymerization of the alicyclic cyclic carbonate is not particularly limited, but examples thereof include acid catalysts, base catalysts, and enzyme catalysts.
• base catalysts include, but are not limited to, alkali metals, metal alkoxides, metal organic acid salts, cyclic amines, triamine compounds, and heterocyclic compounds. Among these, alkali metals and metal alkoxides are preferred.
• the method of reacting an alicyclic cyclic carbonate in the presence of an initiator is not particularly limited. You may use such a method.
• alicyclic cyclic oxide used for copolymerization with carbon dioxide one type of alicyclic cyclic oxide may be used alone. Any two or more alicyclic cyclic oxides having different R 1 to R 6 may be used in combination.
• the polymerization catalyst for copolymerizing carbon dioxide and an alicyclic cyclic oxide is not particularly limited, but examples thereof include metal catalysts such as aluminum catalysts and zinc catalysts. Among these, zinc catalysts are preferred, and organic zinc catalysts are more preferred, in terms of reactivity between alicyclic cyclic oxides and carbon dioxide.
• the method of reacting the alicyclic cyclic oxide and carbon dioxide in the presence of a polymerization catalyst is not particularly limited, but for example, after mixing the alicyclic cyclic oxide and the polymerization catalyst in an autoclave. , and a method of injecting carbon dioxide for reaction.
• Transesterification method In the method for producing the polycarbonate resin used in the present embodiment, as the alicyclic cyclic diol used in the transesterification method, one type of alicyclic cyclic diol may be used alone, and R 1 to Any two or more alicyclic cyclic diols having different R6 may be used in combination.
• the carbonate precursor is not particularly limited, for example, carbonate esters, carbonyl halides, etc. are used. Specifically, although not particularly limited, diphenyl carbonate, dimethyl carbonate, phosgene, etc., can be mentioned.
• the polymerization catalyst for forming an alicyclic cyclic diol is not particularly limited, but examples thereof include alkali metal hydroxides, alkali metal carbonates and organic amines. Among these, alkali metal hydroxides are preferred.
• the method of reacting the alicyclic cyclic diol and the carbonate precursor in the presence of a polymerization catalyst is not particularly limited, but any commonly used polymerization method such as melt polymerization or solid phase polymerization may be used. Any method can be used.
• the method for producing the polycarbonate resin used in the present embodiment includes a purification step.
• the purification method is not particularly limited, but examples thereof include devolatilization purification by heating under reduced pressure and precipitation purification using a precipitation solvent.
• one of the above purification steps may be used alone, or two of them may be used in combination.
• devolatilization purification In the purification step of the polycarbonate resin used in the present embodiment, devolatilization purification may or may not be used.
• the devolatilization purification conditions are not particularly limited as long as they are within a range in which the polycarbonate resin used in the present embodiment can be purified. is 100-270°C.
• the devolatilization pressure is preferably 0 to 80 kPaA, more preferably 0 to 50 kPaA, still more preferably 0 to 10 kPaA.
• Precipitation purification may or may not be used in the purification step of the polycarbonate resin used in the present embodiment.
• Precipitation purification conditions are not particularly limited as long as the polycarbonate resin used in the present embodiment can be purified, but the precipitation solvent is preferably methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, Alcohol solvents such as decanol can be mentioned.
• the polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond, particularly from the viewpoint of significantly increasing thermal stability in nitrogen.
• the compound having an amide bond used in the present embodiment is not particularly limited as long as it is a compound having an amide bond in the molecule. Examples thereof include fatty acid amides, phenylamide stabilizers, and oxalic acid anilide stabilizers.
• the compound having an amide bond is a compound having a structure represented by the following formula (2), a compound having a structure represented by the following formula (3), or a compound having a structure represented by the following formula (4).
• a compound having a structure represented by the following formula (2) is a compound having a structure represented by the following formula (2), a compound having a structure represented by the following formula (3), or a compound having a structure represented by the following formula (4).
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms.
• the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group.
• R 13 is an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms
• R 11 and R 12 are each independent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, the alkylene group, the alkenylene group, the alkoxylylene group, the alkyl group, the alkenyl group, the alkoxy group, and the cycloalkyl groups, said a
• the aryl group and the heteroaryl group may be substituted with an alkyl group having 1 to 6 carbon atoms, and the aralkyl group, the aryl group and the heteroaryl group each have a carbon number It may be substituted with 1 to 20 alkyl groups.
• fatty acid amides include, but are not limited to, N-vinylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N-methylpropionamide, 2-amino-N-methylacetamide, 2-hydroxy-N- methylacetamide, N-hydroxymethylacetamide, 2-chloro-N-methylacetamide, 2-bromo-N-methylacetamide, imidazolidion-4-one hydrochloride, N,N-dimethylprop-2-ynamide, N , N-diethylprop-2-ynamide, 1,2-diacetylhydrazine, 4-oxo-4-[N'-(thiophene-2-carbonyl)-hydrazino]butyric acid, stearic acid amide, oleic acid amide, erucic acid amide , ethylenebisstearic acid amide, methylenebisstearic acid amide, ethylenebis oleic acid amide, and the like
• phenylamide stabilizer examples include, but are not limited to, N-(2H-1,2,4-triazol-5-yl) salicylamide, dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide]. , 2′,3′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N′-hexamethylenebis[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propanamide], N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide and the like.
• oxalic acid anilide heat stabilizer examples include, but are not limited to, 2-ethoxy-2'-ethyl oxalic acid bisanilide, N-(2-ethylphenyl)-N'-(2-ethoxyphenyl) oxalic acid diamide. , 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]henicosan-21-one.
• the compound having an amide bond used in the present embodiment is preferably a phenylamide stabilizer. , more preferably a compound having a structure represented by the above formula (4), more preferably 2′,3′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl ] hydrazine. These may be used singly or in combination of two or more.
• the compound having an amide bond used in the present embodiment is preferably a compound having a structure represented by the above formula (2) or a compound having the above formula (3) and more preferably N-(2H-1,2,4-triazol-5-yl) salicylamide or dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide] is mentioned.
• Increasing thermal stability in air tends to improve product thermal stability in air, for example.
• the content of the compound having an amide bond used in the polycarbonate resin composition of the present embodiment is preferably the total mass of the polycarbonate resin composition, from the viewpoint of the amount of addition that can sufficiently obtain the effects of the present invention, and the cost.
• the polycarbonate resin composition of the present embodiment preferably contains a sulfur compound from the viewpoint of significantly increasing the thermal stability in air.
• the sulfur compound is not particularly limited as long as it is a compound having sulfur in the molecule, and examples thereof include methyl mercaptoacetate, ethyl mercaptoacetate, ethyl 2-(methylthio)acetate, methyl cysteine, methoxycarbonylsulfenyl chloride, and 2-ethylsulfanyl.
• ditridecyl 3,3′-thiobispropionate tetrakis[3-(dodecylthio)propionate]pentaerythritol.
• R 13 and R 14 are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkoxylylene group having 1 to 20 carbon atoms.
• R 11 and R 12 each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• the alkylene group an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms
• the alkylene group the alkenylene group, the alkoxylene group, the alkyl group, the alkenyl group, the alkoxy group
• the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group
• the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.
• m represents an integer of 1 to 4
• each R 12 is independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or 1 to 1 carbon atoms.
• 20 alkoxylene groups and each R 11 is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms.
• R 13 is an m-valent hydrocarbon group optionally having an alkoxy group
• the alkylene group, the alkenylene group, the alkoxylen group, the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group are hydroxyl groups
• phosphorus may be substituted with an acid group, an amino group, an alkoxy group, or an ester group
• the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms; .
• the content of the sulfur compound is the amount that can sufficiently obtain the effect of the present invention, and from the viewpoint of cost, the total mass of the polycarbonate resin composition.
• it is preferably 500 mass ppm to 10000 mass ppm, more preferably 500 mass ppm to 5000 mass ppm, still more preferably 1000 mass ppm to 5000 mass ppm.
• the polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond and a sulfur compound from the viewpoint of remarkably improving thermal stability in air and nitrogen.
• the content of the compound having an amide bond and the sulfur compound is an amount sufficient to obtain the effects of the present invention.
• each preferably 500 mass ppm to 10000 mass ppm, more preferably 500 mass ppm to 5000 mass ppm, still more preferably 1000 mass ppm to 5000 mass ppm, relative to the total mass of the polycarbonate resin composition. is.
• the polycarbonate resin composition of the present embodiment preferably contains a phosphite ester compound from the viewpoint of significantly increasing the thermal stability in nitrogen.
• the phosphite ester compound has a phosphite ester in the molecule, and from the viewpoint of generating sufficient interaction between the carbonate and the phosphite ester, bulky substituents are added near the ether in the phosphite ester compound.
• Any compound that does not have Phosphite ester compounds include, but are not limited to, trimethylphosphite, triethylphosphite, triallylphosphite, triisopropylphosphite, tributylphosphite, trihexylphosphite, tri(2-ethylhexyl)phosphite, phyto, triisodecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, 1,2-phenylene phosphorochloridite, 2-chloro-4H-1,3, 2-benzodioxaphosphorin-4-one, tris( ⁇ -chloroethyl)phosphite, diphenylmethylphosphite, triphenylphosphite, ethylhexyldiphenyl
• m represents an integer of 0 to 3
• R 11 to R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. , an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.
• the alkyl group, the alkenyl group, the alkoxy group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group are substituted by a hydroxyl group, a phosphate group, an amino group, an alkoxy group, or an ester group.
• the aralkyl group, the aryl group, and the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.
• m represents an integer of 1 to 4
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. , an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.
• R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or a cycloalkyl group having 7 to 20 carbon atoms.
• R 15 is an m-valent hydrocarbon group, the alkyl group, the alkenyl group, the alkoxy group,
• the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group may be substituted with a hydroxyl group, a phosphoric acid group, an amino group, an alkoxy group, or an ester group.
• the heteroaryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.
• the content of the phosphite ester compound is the amount that can sufficiently obtain the effects of the present invention, and from the viewpoint of cost, the polycarbonate resin It is preferably 500 mass ppm to 10000 mass ppm, more preferably 500 mass ppm to 5000 mass ppm, still more preferably 1000 mass ppm to 5000 mass ppm, relative to the total mass of the composition.
• the polycarbonate resin composition of the present embodiment preferably contains a compound having an amide bond and a phosphite ester compound from the viewpoint of significantly increasing thermal stability in nitrogen.
• the content of the compound having an amide bond and the phosphite compound is sufficient to achieve the effects of the present invention.
• each is preferably 500 ppm by mass to 10000 ppm by mass, more preferably 500 ppm by mass to 5000 ppm by mass, and still more preferably 1000 ppm by mass, relative to the total mass of the polycarbonate resin composition. Mass ppm to 5000 mass ppm.
• additives in the polycarbonate resin composition of the present embodiment include neutralizers, ultraviolet absorbers, release agents, colorants, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers, A retardant, a bluing agent, a fluidity modifier, etc. may be added.
• one or more compounds selected from the group consisting of a compound having an amide bond, a sulfur compound, and a phosphite ester compound (hereinafter simply referred to as an "additive compound") are added to the polycarbonate resin.
• the timing of mixing, and the method of mixing are not particularly limited. From the viewpoint of preventing thermal decomposition, the timing of mixing is preferably, for example, after addition of the polymerization terminator and after precipitation and purification.
• the method for adding the additive compound to the polycarbonate resin is not particularly limited, but examples include a kneader, a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a roll machine, and an extruder. or a solution blending method of mixing in a state of being dissolved in a common good solvent such as acetone.
• the column temperature was set to 40° C., tetrahydrofuran was used as the mobile phase, and analysis was performed at a rate of 0.60 mL/min.
• An RI detector was used as a detector.
• Polystyrene standard samples manufactured by Polymer Standards Service (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) were used as standard samples to prepare a calibration curve. Based on the calibration curve prepared in this manner, the number average molecular weight and weight average molecular weight of the polycarbonate resin were obtained.
• the glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name “DSC8500”) manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL/min. More specifically, after holding at 40° C. for 3 minutes, the temperature was first raised from 40° C. to 200° C. at 20° C./min to completely melt the sample. After that, the temperature was lowered from 200° C. to 40° C. at 50° C./min and held at 40° C. for 5 minutes. Subsequently, a step-like change partial curve of the DSC curve drawn when the temperature is increased from 40° C. to 190° C. at 10° C./min. was taken as the glass transition temperature (Tg).
• DSC8500 differential scanning calorimeter
• Example 1 Polycarbonate resin (A-1) 1.0 g so as to have the composition shown in Table 1, and 2.0 g of an acetone solution containing 1000 ppm of a compound (B-1) having an amide bond, using a magnetic stirrer. The mixture was mixed and dried under vacuum at 100° C. for 2 hours to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was press-molded with a hydraulic press at 20 MPaG to obtain a plate-like test piece of the polycarbonate resin composition. Table 1 shows the results of thermal stability measurement evaluated using the obtained test piece.
• Examples 2-3 A polycarbonate resin composition was obtained in the same manner as in Example 1, except that the formulation of the additive (compound having an amide bond) was changed as shown in Table 1. The obtained polycarbonate resin composition was evaluated after forming a test piece in the same manner as in Example 1, and the results are shown in Table 1.
• the polycarbonate resin compositions of Examples 1 to 3 have a higher thermal decomposition initiation temperature and improved thermal stability than the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 1 to 7. Do you get it.
• the column temperature was set to 40° C., tetrahydrofuran was used as the mobile phase, and analysis was performed at a rate of 0.60 mL/min.
• An RI detector was used as a detector.
• Polystyrene standard samples manufactured by Polymer Standards Service (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) were used as standard samples to prepare a calibration curve. Based on the calibration curve prepared in this way, the weight average molecular weight of the polycarbonate resin was obtained.
• the glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name “DSC8500”) manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL/min. More specifically, after holding at 40° C. for 3 minutes, the temperature was first raised from 40° C. to 200° C. at 20° C./min to completely melt the sample. After that, the temperature was lowered from 200° C. to 40° C. at 50° C./min and held at 40° C. for 5 minutes.
• DSC8500 differential scanning calorimeter
• a polycarbonate resin composition The abbreviations of the compounds used in the following examples and comparative examples are as follows.
• B-1 Ditridecyl 3,3'-thiobispropionate
• B-2 Tetrakis[3-(dodecylthio)propionate] pentaerythritol
• ((C) antioxidant) C-1: Hindered phenolic compound (Irganox 1010 manufactured by BASF)
• C-2 Hindered phenol compound (Irganox 1076 manufactured by BASF)
• C-3 Hindered phenol compound (SUMILIZER GA-80 manufactured by Sumitomo Chemical Co., Ltd.)
• C-4 Phosphite compound (Irgafos 168 manufactured by BASF)
• C-5 Phosphite compound (adekastab PEP-36 manufactured by ADEKA)
• Example 4 1.0 g of the polycarbonate resin (A-1) and 2.0 g of an acetone solution containing 1000 ppm of the sulfur compound (B-1) were mixed using a magnetic stirrer so as to have the composition shown in Table 2, It was dried under vacuum at 100° C. for 2 hours to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was press-molded with a hydraulic press at 20 MPaG to obtain a plate-like test piece of the polycarbonate resin composition. Table 2 shows the measurement and evaluation results of thermal stability using the obtained test piece.
• Example 5 A polycarbonate resin composition was obtained in the same manner as in Example 4, except that the formulation of the additive (sulfur compound) was changed as shown in Table 2. After preparing a test piece in the same manner as in Example 4, the obtained polycarbonate resin composition was measured and evaluated. Table 2 shows the results.
• the polycarbonate resin compositions of Examples 4 and 5 have a higher thermal decomposition initiation temperature and improved thermal stability than the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 8 to 14. Do you get it.
• the column temperature was set to 40° C., tetrahydrofuran was used as the mobile phase, and analysis was performed at a rate of 0.60 mL/min.
• An RI detector was used as a detector.
• Polystyrene standard samples manufactured by Polymer Standards Service (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) were used as standard samples to prepare a calibration curve. Based on the calibration curve prepared in this way, the weight average molecular weight of the polycarbonate resin was determined.
• the glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name “DSC8500”) manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL/min. More specifically, after holding at 40° C. for 3 minutes, the temperature was first raised from 40° C. to 200° C. at 20° C./min to completely melt the sample. After that, the temperature was lowered from 200° C. to 40° C. at 50° C./min and held at 40° C. for 5 minutes.
• DSC8500 differential scanning calorimeter
• a polycarbonate resin composition The abbreviations of the compounds used in the following examples and comparative examples are as follows.
• B-1 2',3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
• B-2 N-(2H-1,2,4-triazole- 5-yl) salicylamide
• Example 6 1.0 g of polycarbonate resin (A-1), 2.0 g of acetone solution containing 1000 ppm of compound (B-1) having an amide bond, and 1000 ppm of sulfur compound (C-1) so as to have the composition shown in Table 3. 2.0 g of the acetone solution contained was mixed using a magnetic stirrer and dried under vacuum at 100° C. for 2 hours to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was press-molded with a hydraulic press at 20 MPaG to obtain a plate-like test piece of the polycarbonate resin composition. Table 3 shows the results of thermal stability measurement evaluated using the obtained test pieces.
• the thermal decomposition initiation temperature is +3 based on the highest thermal decomposition initiation temperature. °C or higher has the effect of improving thermal stability (marked as " ⁇ ” in Table 3), and when the thermal decomposition start temperature is less than +3 °C, there is no effect of improving thermal stability (marked with " ⁇ " in Table 3 marked).
• Example 7-8 A polycarbonate resin composition was obtained in the same manner as in Example 6, except that the formulation of the additives was changed as shown in Table 4. The obtained polycarbonate resin composition was evaluated after forming a test piece in the same manner as in Example 6, and the results are shown in Table 4. Among the measurement results of the thermal stability of the test pieces of the polycarbonate resin compositions of Comparative Examples 15 and 17 to 19, the thermal decomposition initiation temperature is based on the one with the highest thermal decomposition initiation temperature. If the temperature is +3 ° C. or higher, there is an effect of improving thermal stability (marked as " ⁇ " in Table 4). ), was determined.
• a polycarbonate resin composition was obtained in the same manner as in Example 6, except that the formulation of the additives was changed as shown in Table 3 or Table 4.
• the obtained polycarbonate resin composition was evaluated after forming a test piece in the same manner as in Example 6, and the results are shown in Table 3 or Table 4.
• Example 6 has improved thermal stability compared to the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 15, 16 and 19.
• the polycarbonate resin compositions of Examples 7 to 8 have a higher thermal decomposition initiation temperature and higher thermal stability than the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 15 and 17 to 19. found to improve.
• the column temperature was set to 40° C., tetrahydrofuran was used as the mobile phase, and analysis was performed at a rate of 0.60 mL/min.
• An RI detector was used as a detector.
• Polystyrene standard samples manufactured by Polymer Standards Service (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) were used as standard samples to prepare a calibration curve. Based on the calibration curve prepared in this way, the weight average molecular weight of the polycarbonate resin was determined.
• the glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name “DSC8500”) manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL/min. More specifically, after holding at 40° C. for 3 minutes, the temperature was first raised from 40° C. to 200° C. at 20° C./min to completely melt the sample. After that, the temperature was lowered from 200° C. to 40° C. at 50° C./min and held at 40° C. for 5 minutes.
• DSC8500 differential scanning calorimeter
• a polycarbonate resin composition The abbreviations of the compounds used in the following examples and comparative examples are as follows.
• B-1 triphenyl phosphite ester compound
• B-2 tetraalkyl (C12-15)-4,4'-isopropylidene diphenyl diphosphite
• B-3 tris noniphenyl phosphite
• ((C) antioxidant) C-1: Hindered phenolic compound (Irganox 1010 manufactured by BASF)
• C-2 Hindered phenol compound (Irganox 1076 manufactured by BASF)
• C-3 Hindered phenol compound (SUMILIZER GA-80 manufactured by Sumitomo Chemical Co., Ltd.)
• C-4 Phosphite compound (Irgafos 168 manufactured by BASF)
• C-5 Phosphite compound (adekastab PEP-36 manufactured by ADEKA)
• Example 9 1.0 g of the polycarbonate resin (A-1) and 2.0 g of an acetone solution containing 1000 ppm of the phosphite ester compound (B-1) so as to have the composition shown in Table 5 were stirred using a magnetic stirrer. The mixture was mixed and dried under vacuum at 100° C. for 2 hours to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was press-molded with a hydraulic press at 20 MPaG to obtain a plate-like test piece of the polycarbonate resin composition. Table 5 shows the measurement and evaluation results of thermal stability using the obtained test piece.
• Example 10-11 A polycarbonate resin composition was obtained in the same manner as in Example 9, except that the formulation of the additive (phosphite ester compound) was changed as shown in Table 5. The obtained polycarbonate resin composition was measured and evaluated after forming a test piece in the same manner as in Example 9. Table 5 shows the results.
• the polycarbonate resin compositions of Examples 9 to 11 have a higher thermal decomposition initiation temperature and improved thermal stability than the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 20 to 26. Do you get it.
• the column temperature was set to 40° C., tetrahydrofuran was used as the mobile phase, and analysis was performed at a rate of 0.60 mL/min.
• An RI detector was used as a detector.
• Polystyrene standard samples manufactured by Polymer Standards Service (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) were used as standard samples to prepare a calibration curve. Based on the calibration curve prepared in this way, the weight average molecular weight of the polycarbonate resin was obtained.
• the glass transition temperature Tg of the polycarbonate resin was measured using a differential scanning calorimeter (product name “DSC8500”) manufactured by PerkinElmer Japan Co., Ltd. under the condition of a nitrogen gas flow rate of 20 mL/min. More specifically, after holding at 40° C. for 3 minutes, the temperature was first raised from 40° C. to 200° C. at 20° C./min to completely melt the sample. After that, the temperature was lowered from 200° C. to 40° C. at 50° C./min and held at 40° C. for 5 minutes.
• DSC8500 differential scanning calorimeter
• a polycarbonate resin composition The abbreviations of the compounds used in the following examples and comparative examples are as follows.
• Example 12 1.0 g of a polycarbonate resin (A-1), 2.0 g of an acetone solution containing 1000 ppm of a compound (B-1) having an amide bond, a phosphite ester compound (C- 2.0 g of an acetone solution containing 1000 ppm of 1) was mixed using a magnetic stirrer and dried under vacuum at 100° C. for 2 hours to obtain a polycarbonate resin composition.
• the resulting polycarbonate resin composition was press-molded with a hydraulic press at 20 MPaG to obtain a plate-like test piece of the polycarbonate resin composition.
• Table 6 shows the measurement and evaluation results of thermal stability using the obtained test pieces.
• Example 13-14 A polycarbonate resin composition was obtained in the same manner as in Example 12, except that the formulation of the additives was changed as shown in Table 6. The obtained polycarbonate resin composition was measured and evaluated after forming a test piece in the same manner as in Example 12. Table 6 shows the results.
• the polycarbonate resin compositions of Examples 12 to 14 have a higher thermal decomposition initiation temperature and improved thermal stability than the polycarbonate resins and polycarbonate resin compositions of Comparative Examples 27 to 31. Do you get it.
• the polycarbonate resin composition of the present invention has excellent thermal stability and tends to have excellent optical properties such as good moldability, hue, and transparency, and is used for optical lens materials, optical devices, optical component materials, and display materials. It has industrial applicability in the field of various optical materials such as

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