Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • 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

Definitions

• the present invention relates to polycarbonate resin with excellent scratch resistance and heat resistance, and molded articles made from the same.
• Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability, and is therefore used as an engineering plastic in a wide range of fields, including the housings of electrical and electronic devices, interior and exterior parts of automobiles, building materials, furniture, musical instruments, and miscellaneous goods. Furthermore, compared to inorganic glass, it has a lower specific gravity, making it possible to reduce weight and offering excellent productivity, which is why it is used for windows in automobiles, etc.
• sheets and films made from polycarbonate resin are widely used as various display devices and protective parts for automobile interiors by applying additional secondary processing such as coating, lamination, and surface modification.
• Patent Document 7 describes a method for producing polycarbonates and copolycarbonates that contain 2,2-bis(4-hydroxy-3-methylphenyl)fluorene as a repeating unit, and suggests that this is effective in achieving high pencil hardness and high heat resistance. However, this method has the problem of insufficient scratch resistance.
• the present invention aims to solve these problems by providing a polycarbonate resin with excellent scratch resistance and heat resistance, and a molded product made from the same.
• Patent No. 5173803 Japanese Patent Application Laid-Open No. 64-069625 Japanese Patent Application Laid-Open No. 08-183852 Japanese Patent Application Laid-Open No. 08-034846 JP 2002-117580 A Patent No. 3768903 International Publication No. 2017/073508
• the problem that this invention aims to solve is to provide a polycarbonate resin with excellent heat resistance and scratch resistance, and a molded article made from the same.
• the present invention is as follows:
• ring Z is a condensed polycyclic arene ring
• R1 and R2 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• R 3 and R 4 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of
• R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different;
• R 13 and R R 15 , R 16 , R 17 and R 18 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atom
• R 29 , R 30 , and R 31 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when there are a plurality of each, they may be the same or different, and k is an integer of 1 to 3.) 5.
• repeating unit (B) represented by formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine.
• the molded product according to paragraph 14 above which has a spectral light transmittance of 85% or more at wavelengths of 850 nm, 1310 nm, and 1550 nm, 82% or more at wavelength 1610 nm, and 78% or more at wavelength 1625 nm.
• ring Z is a condensed polycyclic arene ring
• R1 and R2 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• R 3 and R 4 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of
• R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different;
• R 13 and R R 15 , R 16 , R 17 and R 18 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atom
• the polycarbonate resin of the present invention and the molded products made from it have excellent scratch resistance and heat resistance, making them suitable for use in automobile interior parts. Therefore, the industrial effects they bring about are exceptional.
• the polycarbonate resin in the present invention is a polycarbonate resin containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2).
• ring Z is a condensed polycyclic arene ring
• R1 and R2 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• R 3 and R 4 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of
• R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different;
• R 13 and R R 15 , R 16 , R 17 and R 18 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atom
• examples of the fused polycyclic arene ring represented by ring Z include fused bicyclic arene rings (e.g., fused bicyclic arene rings having 10 to 16 carbon atoms, such as a naphthalene ring or an indene ring), and fused tricyclic arene rings (e.g., anthracene ring or a phenanthrene ring).
• Ring Z is preferably a naphthalene ring or anthracene ring, and more preferably a naphthalene ring.
• the two rings Z connected to the carbon atom at position 9 of the fluorene ring may be different from each other, but are usually the same in many cases.
• substitution position of ring Z relative to the 9-position of the fluorene ring is not particularly limited.
• the substitution may be at either the 1-position or the 2-position of the naphthalene ring relative to the 9-position of the fluorene ring, and substitution at the 2-position is preferred.
• the ring Z is a naphthalene ring
• they are usually substituted at any of the 5-8 positions of the naphthyl group that is bonded at the 1- or 2-position to the 9-position of the fluorene ring
• the 1- or 2-position of the naphthalene ring is substituted for the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship)
• R 1 and R 2 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, etc.
• alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups.
• Alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and octoxy groups. Alkoxy groups having 1 to 6 carbon atoms are preferred.
• Cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.
• cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyloxy groups. Cycloalkoxy groups having 6 to 12 carbon atoms are preferred.
• Alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred.
• Aryl groups having 6 to 14 carbon atoms include phenyl and naphthyl groups.
• Aryloxy groups having 6 to 14 carbon atoms include phenyloxy and naphthyloxy groups.
• aralkyl groups having 7 to 20 carbon atoms examples include benzyl and phenylethyl groups.
• aralkyloxy groups having 7 to 20 carbon atoms examples include benzyloxy groups and phenylethyloxy groups.
• R 1 and R 2 are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and particularly preferably a hydrogen atom.
• the content of repeating unit (A) is 1 to 99 mol % of the total repeating units of the polycarbonate resin, preferably 5 to 95 mol %, and more preferably 10 to 90 mol %.
• the pencil hardness and indentation hardness are high, resulting in excellent scratch resistance, and the glass transition temperature and 5% weight loss temperature are excellent, resulting in good heat resistance, which is preferable.
• R 3 and R 4 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each of them, they may be the same or different.
• examples of the alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the cycloalkyl group having 6 to 20 carbon atoms, the cycloalkoxy group having 6 to 20 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms, the aryloxy group having 6 to 14 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, and the aralkyloxy group having 7 to 20 carbon atoms include the same as those described above.
• W is a single bond or at least one group selected from the group consisting of groups represented by the formula (3).
• R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of them, they may be the same or different.
• alkyl groups having 1 to 18 carbon atoms examples include those mentioned above.
• R 13 and R 14 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• alkyl groups having 1 to 18 carbon atoms examples include those mentioned above.
• R 15 , R 16 , R 17 and R 18 each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of such groups, they may be the same or different.
• alkyl groups having 1 to 18 carbon atoms examples include those mentioned above.
• c is an integer from 1 to 10, preferably an integer from 1 to 4, and more preferably 1.
• d is an integer from 4 to 7, and preferably 5.
• h and i are integers from 1 to 3, and preferably 1.
• g is an integer from 1 to 100, preferably an integer from 10 to 90, and more preferably an integer from 20 to 80.
• W contains at least one group selected from the group consisting of groups represented by the following formula (4):
• R 29 , R 30 , and R 31 each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and when there are a plurality of each, they may be the same or different, and k is an integer of 1 to 3.
• R 29 , R 30 and R 31 each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups.
• R 29 and R 30 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
• R 31 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.
• the repeating unit (B) represented by the formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as BPC), 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPA), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (hereinafter sometimes abbreviated as PPPBP).
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• BPA 2,2-bis(4-hydroxyphenyl)propane
• BisP-HTG 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
• PPPBP 2-phenyl-3,3-bis(p-hydroxy
• the content of repeating unit (B) is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, and even more preferably 10 to 90 mol% of the total repeating units of the polycarbonate resin. If it is within the above range, the pencil hardness and indentation hardness will be high, resulting in excellent scratch resistance, and the glass transition temperature and 5% weight loss temperature will be excellent, resulting in good heat resistance, which is preferable.
• the polycarbonate resin in the present invention may contain, in addition to the repeating units (A) and (B), repeating units derived from other dihydroxy compounds or other diol compounds, as described below, to the extent that the properties of the polycarbonate resin are not impaired.
• the repeating units (C) other than the repeating units (A) and (B) are preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 5 mol % or less, based on the total repeating units.
• the repeating unit (A) represented by the formula (1) is derived from a diol compound, and specifically, 9,9-bis(6-hydroxy-2-naphthyl)fluorene or 9,9-bis(6-hydroxy-1-naphthyl)fluorene is preferable, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene is more preferable.
• These diol compounds may be used alone or in combination of two or more.
• the repeating unit (B) represented by the formula (2) is derived from a diol compound, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3-propylphenyl)propane; 2,2-bis(4-hydroxy-3-butylphenyl)propane; bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)butane; 2,2-bis(4-hydroxyphenyl)octane; 2,2-bis(4-hydroxyphenyl)phenylmethane; 2,2-bis(4-hydroxy-3-methylphenyl)phenylmethane; 2,2-bis(4-hydroxy- 1-methylphenyl)propane; bis(4-hydroxyphenyl)naphthy
• 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane or ⁇ , ⁇ '-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine are preferred, and 2,2-bis(4-hydroxyphenyl)propane (BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (PPPBP) are even more preferred.
• BPA 2,2-bis(4-hydroxyphenyl)propane
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)prop
• the polycarbonate resin of the present invention may be copolymerized with other dihydroxy compounds or diol compounds in addition to the repeating units (A) and (B) to the extent that the properties of the polycarbonate resin are not impaired.
• dihydroxy compounds include hydroquinone, resorcinol, orcinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane; 2,2-bis(4-hydroxyphenyl)adamantane; 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaenebisphenoxyethanolfluorene, etc.
• diol compounds include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis/trans-1,4-cyclohexanedimethanol (CHDM), cis/trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanoate, Examples of such cyclohexanedimethanol include 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).
• TCDDM tricyclode
• the polycarbonate resin in the present invention is obtained by reacting the diol compound with the carbonate precursor.
• the reaction method may include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
• interfacial polycondensation a terminal terminator of a monohydric phenol is usually used.
• Polycarbonate resins include polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids.
• the aliphatic bifunctional carboxylic acids are preferably ⁇ , ⁇ -dicarboxylic acids.
• Preferred examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the purpose is not hindered.
• the polycarbonate resin may be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.
• polycarbonate resins can be copolymerized with structural units containing trifunctional or higher polyfunctional aromatic compounds to form branched polycarbonates.
• trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include trisphenols such as 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4- ⁇ 4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol.
• trisphenols such as 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptan
• 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.
• the constituent units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol%, of a total of 100 mol% including the constituent units from other diol components.
• the branched structural unit may be derived not only from a polyfunctional aromatic compound, but also from a side reaction occurring during a polymerization reaction by a melt transesterification method without using a polyfunctional aromatic compound.
• the proportion of such branched structures can be calculated by 1H -NMR measurement.
• the reaction is usually carried out in the presence of an acid binder and a solvent.
• an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine, is used.
• the solvent for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used.
• a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction.
• the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
• Transesterification using, for example, a carbonic acid diester as a carbonate precursor is carried out by heating and stirring a predetermined ratio of aromatic diol components with a carbonic acid diester under an inert gas atmosphere, and distilling off the resulting alcohol or phenol.
• the reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C.
• the reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol.
• a catalyst usually used in transesterification can also be used to promote the reaction.
• carbonic acid diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
• Monofunctional phenols that are commonly used as end terminators can be used.
• monofunctional phenols are generally used as end terminators for molecular weight control, and the obtained polycarbonate resin has excellent thermal stability compared to those not having the end terminator, since the end is blocked by a group based on a monofunctional phenol.
• the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.
• the polycarbonate resin in the present invention may contain various additives to give various properties to the resin composition within a range that does not impair the object of the present invention.
• the additives may include a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat shielding agent, a fluorescent dye (including a fluorescent brightener), a pigment, a light diffusing agent, a reinforcing filler, other resins, elastomers, etc.
• the release agent is preferably one that is composed of 90% by weight or more of an ester of alcohol and fatty acid.
• Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid.
• Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Stearyl stearate is preferred.
• esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, and other complete or partial esters of dipentaerythritol.
• esters stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred, and stearic acid monoglyceride and pentaerythritol tetrastearate are more preferred.
• the amount of release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably in the range of 0.1 to 0.4 parts by weight, and even more preferably in the range of 0.12 to 0.3 parts by weight, per 100 parts by weight of polycarbonate resin.
• Heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers.
• Phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
• Specific examples include bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)diphosphite, ...
• the amount of the heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably in the range of 0.005 to 0.4 parts by weight, and even more preferably in the range of 0.01 to 0.3 parts by weight, based on 100 parts by weight of the polycarbonate resin.
• the viscosity average molecular weight of the polycarbonate resin in the present invention is preferably in the range of 6,000 to 350,000, more preferably in the range of 7,000 to 30,000, even more preferably in the range of 8,000 to 28,000, particularly preferably in the range of 9,000 to 25,000, and most preferably in the range of 10,000 to 22,000. If it is in the above range, it is preferable because it has excellent scratch resistance, heat resistance, and moldability.
• the glass transition temperature (Tg) of the polycarbonate resin in the present invention is preferably in the range of 125 to 310°C, more preferably in the range of 125 to 300°C, even more preferably in the range of 130 to 290°C, particularly preferably in the range of 135 to 280°C, and most preferably in the range of 140 to 270°C.
• Tg Glass transition temperature
• the glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Ltd. at a heating rate of 20°C/min. (5% weight loss temperature: Td5%)
• the lower limit of the 5% weight loss temperature (Td5%) of the polycarbonate resin in the present invention is preferably 400°C or higher, more preferably 410°C or higher, and even more preferably 420°C or higher. If the 5% weight loss temperature is higher than the lower limit, the heat resistance, thermal stability, and moldability are good, which is preferable.
• the upper limit is not particularly limited, but is preferably 700°C or lower, more preferably 600°C or lower, and even more preferably 500°C or lower.
• the 5% weight loss temperature is measured using a TGA (model TGA2950) manufactured by TA Instruments.
• the pencil hardness of the polycarbonate resin in the present invention is preferably 2H or more, more preferably 3H or more.
• the pencil hardness is a hardness that does not leave a scratch mark when the polycarbonate resin is rubbed with a pencil having a specific pencil hardness, and it is preferable to use the pencil hardness used in the surface hardness test of the coating film that can be measured according to JIS K-5600 as an index.
• the pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.
• the pencil hardness is above the above level, the molded product has excellent scratch resistance.
• the polycarbonate resin of the present invention preferably has an indentation hardness of 235 to 450 (N/mm 2 ), more preferably 240 to 430 (N/mm 2 ), even more preferably 245 to 420 (N/mm 2 ), particularly preferably 250 to 410 (N/mm 2 ), and most preferably 260 to 400 (N/mm 2 ), as measured in accordance with ISO/TS 19278.
• the indentation hardness is within the above range, the molded article has excellent scratch resistance.
• pencil hardness which is a commonly used index for the scratch resistance of materials, is a discrete index with a range, so it is difficult to compare the hardness of materials with the same pencil hardness of "2H," for example. Therefore, by using indentation hardness, which allows for quantitative evaluation, as an index, it is possible to evaluate the degree of hardness even for materials with the same pencil hardness.
• the indentation hardness is measured based on ISO/TS 19278 by using a dynamic ultra-microhardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between the load and the indentation depth on the surface of the resin plate in real time.
• a method for molding the polycarbonate resin in the present invention a general method for molding a polycarbonate resin can be used, such as injection molding, extrusion molding, compression molding, solution casting, etc.
• a method for molding a molded product by injection molding or a method for molding a sheet or film by extrusion molding is preferably used.
• the polycarbonate resin of the present invention is excellent in scratch resistance, heat resistance, and transparency, and can be used as various molded products.
• it since it has excellent scratch resistance, it does not require coating treatment, and can be suitably used for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts.
• the polycarbonate resin of the present invention is useful as an optical molded product because of its excellent heat resistance, dimensional stability, low water absorption, and light transmittance, and is particularly suitable for use as an optical molded product for optical components such as optical connectors and transceivers that require solder reflow resistance.
• optical molded products include various lenses such as sensor lenses, focusing lenses, collimator lenses, and lens arrays, as well as mirrors, optical waveguides, and wide-angle diffusion elements.
• the repeating unit (B) represented by the formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPA), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (hereinafter sometimes abbreviated as PPPBP).
• BPA 2,2-bis(4-hydroxyphenyl)propane
• BisP-HTG 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
• PPPBP 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine
• the glass transition temperature (Tg) of the polycarbonate resin in the present invention is preferably in the range of 220 to 310° C., more preferably in the range of 230 to 307° C., even more preferably in the range of 240 to 305° C., and most preferably in the range of 250 to 300° C. If the Tg is within the above range, the heat resistance, dimensional stability, and moldability are good, which is preferable.
• the glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Ltd. at a heating rate of 20° C./min.
• the linear expansion coefficient of the polycarbonate resin in the present invention is preferably in the range of 30 to 60 ppm/°C, more preferably 32 to 58 ppm/°C, even more preferably 34 to 56 ppm/°C, and most preferably 35 to 55 ppm/°C. If the linear expansion coefficient is within the above range, dimensional change due to heat is small, which is preferable.
• the linear expansion coefficient is measured three times using a thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Co., Ltd.) with a sample of 4 mm width x 20 mm length at a heating rate of 10°C/min and a cooling rate of 50°C/min, and the linear expansion coefficient in the measurement temperature range of 50 to 90°C is calculated, and the average value is calculated.
• (Saturated water absorption rate) The saturated water absorption of the polycarbonate resin in the present invention is measured in accordance with JIS K7209:2000 and is preferably 0.50% or less, more preferably 0.49% or less, and even more preferably 0.48% or less. If the saturated water absorption is within the above range, the dimensional change due to water absorption is small, which is preferable.
• the lower limit of the saturated water absorption is not particularly limited, but 0.1% or more is sufficient.
• the optical molded article using the polycarbonate resin of the present invention preferably has a spectral light transmittance of 85% or more at a measurement wavelength of 850 nm, 1310 nm, and 1550 nm, 82% or more at a measurement wavelength of 1610 nm, and 78% or more at a measurement wavelength of 1625 nm. When the spectral light transmittance is within the above range, signal attenuation in optical communication is small, which is preferable.
• the optical molded parts were subjected to a temperature profile for solder reflow testing according to IPC/JEDEC J-STD-020C "Moisture/Reflow Sensitivity Classification of Non-Hermetically Sealed Solid State Surface Mount Devices".
• the molded parts were conditioned in a humidity chamber at 60°C/60% RH (relative humidity) for 120 hours, and then heated in an oven according to the temperature profile of IPC/JEDEC J-STD-020C (peak temperature 240°C or 260°C).
• the polycarbonate resin composition of the present invention is a polycarbonate resin composition containing 1 to 99 parts by weight of a copolymeric polycarbonate resin (component A) having a content of repeating units (a) represented by the following formula (1) of 5 to 95 mol % and a content of repeating units (b) represented by the following formula (2) of 95 to 5 mol % relative to all repeating units, and 99 to 1 part by weight of an aromatic polycarbonate resin (component B).
• ring Z is a condensed polycyclic arene ring
• R1 and R2 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.
• R 3 and R 4 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of
• R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different;
• R 13 and R R 15 , R 16 , R 17 and R 18 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atom
• R5 , R6 , R7, R8 , R9 , R10 , R11 , R12 , R13 , R14 , R15 , R16 , R17 , R18 , c, d, h, i, and g are the same as those described in the (Aspect 1) section.
• the repeating unit (b) represented by the formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as BPC) and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (hereinafter sometimes abbreviated as OCZ).
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• OCZ 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane
• the content of repeating unit (b) is 5 to 95 mol % of the total repeating units of the copolymerized polycarbonate resin (component A), preferably 10 to 90 mol %, more preferably 20 to 90 mol %, and even more preferably 30 to 90 mol %. If it is within the above range, it is preferable because the resin composition with polycarbonate resin (component B) does not undergo phase separation during extrusion or molding, causing the resin composition to become cloudy.
• the copolymeric polycarbonate resin (component A) in the present invention may contain, in addition to the repeating units (a) and (b), repeating units derived from other dihydroxy compounds or other diol compounds, as described below, to the extent that the properties of the polycarbonate resin composition are not impaired.
• the repeating units (c) other than the repeating units (a) and (b) are preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, based on the total repeating units.
• the repeating unit (a) represented by the formula (1) is derived from a diol compound, and specifically, 9,9-bis(6-hydroxy-2-naphthyl)fluorene or 9,9-bis(6-hydroxy-1-naphthyl)fluorene is preferable, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene is more preferable.
• These diol compounds may be used alone or in combination of two or more.
• the repeating unit (b) represented by the formula (2) is derived from a diol compound, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3-propylphenyl)propane; 2,2-bis(4-hydroxy-3-butylphenyl)propane; bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)butane; 2,2-bis(4-hydroxyphenyl)octane; 2,2-bis(4-hydroxyphenyl)phenylmethane; 2,2-bis(4-hydroxy-3-methylphenyl)phenylmethane; 2,2-bis(4-hydroxy- 1-methylphenyl)propane; bis(4-hydroxyphenyl)naphthy
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• OCZ 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane
• copolymerized polycarbonate resin (component A) of the present invention other dihydroxy compounds or diol compounds may be copolymerized in addition to the repeating units (a) and (b) to the extent that the properties of the polycarbonate resin composition are not impaired.
• the other dihydroxy compounds are the same as those explained in the section (Embodiment 1).
• the copolymeric polycarbonate resin (component A) in the present invention is obtained by reacting the diol compound with a carbonate precursor.
• the reaction method may include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
• a terminal terminator of a monohydric phenol is usually used.
• the copolymerized polycarbonate resin (component A) contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid.
• the aliphatic bifunctional carboxylic acid is preferably an ⁇ , ⁇ -dicarboxylic acid.
• Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
• carboxylic acids may be copolymerized to the extent that the purpose is not hindered.
• copolymerized polycarbonate resin (component A) may also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.
• the copolymerized polycarbonate resin (component A) can also be copolymerized with a structural unit containing a trifunctional or higher polyfunctional aromatic compound as necessary to form a branched polycarbonate.
• trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include trisphenols such as 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4- ⁇ 4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol.
• trisphenols such as 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptan
• 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.
• the constituent units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol%, of a total of 100 mol% including the constituent units from other diol components.
• the branched structural unit may be derived not only from a polyfunctional aromatic compound, but also from a side reaction occurring during a polymerization reaction by a melt transesterification method without using a polyfunctional aromatic compound.
• the proportion of such branched structures can be calculated by 1H -NMR measurement.
• the reaction is usually carried out in the presence of an acid binder and a solvent.
• an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine, is used.
• the solvent for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used.
• a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction.
• the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
• Transesterification using, for example, a carbonic acid diester as a carbonate precursor is carried out by heating and stirring a predetermined ratio of aromatic diol components with a carbonic acid diester under an inert gas atmosphere, and distilling off the resulting alcohol or phenol.
• the reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C.
• the reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol.
• a catalyst usually used in transesterification can also be used to promote the reaction.
• carbonic acid diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
• Monofunctional phenols that are commonly used as end terminators can be used.
• monofunctional phenols are generally used as end terminators for molecular weight control, and the obtained polycarbonate resin has excellent thermal stability compared to those not having the end terminator, since the end is blocked by a group based on a monofunctional phenol.
• monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.
• the viscosity average molecular weight of the copolymerized polycarbonate resin (component A) in the present invention is preferably in the range of 6,000 to 35,000, more preferably in the range of 7,000 to 30,000, even more preferably in the range of 8,000 to 28,000, particularly preferably in the range of 9,000 to 25,000, and most preferably in the range of 10,000 to 22,000. If it is within the above range, in a resin composition with the polycarbonate resin (component B), phase separation does not occur during extrusion or molding, and the resin composition does not become cloudy, and is preferable in terms of excellent heat resistance, scratch resistance, and impact resistance.
• the glass transition temperature (Tg) of the copolymerized polycarbonate resin (component A) in the present invention is preferably in the range of 100 to 300°C, more preferably in the range of 120 to 280°C, and even more preferably in the range of 130 to 270°C.
• the glass transition temperature (Tg) is measured using a 2910-type DSC manufactured by TA Instruments Japan Ltd. at a heating rate of 20°C/min.
• the aromatic polycarbonate resin (component B) of the present invention may be either a homopolymer or a copolymer.
• the aromatic polycarbonate resin (B) may have a branched structure or a linear structure, or may be a mixture of a branched structure and a linear structure.
• the aromatic polycarbonate resin (B) can be produced using a dihydric phenol as a raw material by any known method, such as the phosgene method, the ester exchange method, or the pyridine method.
• dihydric phenols include bisphenols, and in particular, 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferably used.
• Bisphenol A may be partially or entirely replaced with another dihydric phenol.
• dihydric phenols include hydroquinone, 4,4-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkanes such as bis(4-hydroxyphenyl)methane and 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)ether compounds, alkylated bisphenols such as 2,2-bis(3-methyl-4-hydroxyphenyl)propane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and halogenated bisphenols such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and 2,2-bis(3,5-dichloro-4-hydroxyphen
• an aromatic polycarbonate resin obtained by using bisphenol A in an amount of preferably 50 mol % or more, more preferably 70 mol % or more, further preferably 90 mol % or more, and particularly preferably 100 mol % is desirable.
• the viscosity average molecular weight of the aromatic polycarbonate resin (component B) used in the present invention is not particularly limited, but is preferably in the range of 15,000 to 35,000, more preferably 18,000 to 32,000, in view of the balance between heat resistance, impact resistance, and moldability in the resin composition.
• the viscosity average molecular weight Mv was calculated from the determined specific viscosity ( ⁇ SP ) according to the following formula.
• Tg Glass transition temperature
• the glass transition temperature (Tg) of the aromatic polycarbonate resin (B) is preferably 120 to 180° C., more preferably 140 to 160° C. If the Tg is within the above range, the polycarbonate resin composition obtained has good heat resistance and impact resistance, which is preferable.
• the glass transition temperature (Tg) is measured using a 2910 Model DSC manufactured by TA Instruments Japan Ltd. at a temperature rise rate of 20° C./min.
• the production method is not particularly limited, and known production methods can be used.
• the copolymer polycarbonate resin (A), the aromatic polycarbonate resin (B) and the additives are premixed, then fed into an extruder and melt-kneaded, and the extruded thread is cooled and cut by a pelletizer to produce a pellet-shaped molding material.
• the extruder may be either a single-screw extruder or a twin-screw extruder, but from the viewpoint of productivity and kneading, a twin-screw extruder is preferred.
• twin-screw extruders include KZW15-25MG (manufactured by Technobel Co., Ltd.) and ZSK (manufactured by Werner & Pfleiderer).
• Specific examples of similar types include TEX (manufactured by Japan Steel Works, Ltd.), TEM (manufactured by Toshiba Machine Co., Ltd.), and KTX (manufactured by Kobe Steel, Ltd.).
• one having a vent that can degas the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used.
• a vacuum pump is preferably installed from the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder.
• the additives can be fed independently to the extruder, it is preferable to premix them with the resin raw material as described above.
• premixing means include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer.
• a more suitable method is, for example, to mix a portion of the raw material with the additives in a high-speed mixer such as a Henschel mixer to create a master agent, and then to mix this master agent with the remaining resin raw material in a low-speed mixer such as a Nauta mixer.
• the resin extruded from the extruder is either directly cut and pelletized, or formed into strands, which are then cut and pelletized by a pelletizer. If it is necessary to reduce the effects of external dust, it is preferable to purify the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, it is preferable to narrow the shape distribution of the pellets, further reduce miscuts, further reduce fine powder generated during transportation or shipping, and reduce air bubbles (vacuum air bubbles) generated inside the strands and pellets using various methods that have already been proposed.
• Miscuts can be reduced by means of temperature management of the thread when cutting with a pelletizer, blowing ion wind when cutting, optimizing the rake angle of the pelletizer, and appropriately blending a release agent, as well as a method of filtering a mixture of cut pellets and water to separate the pellets from the water and miscuts.
• An example of a measurement method is disclosed in, for example, JP 2003-200421 A. These prescriptions can achieve high cycle molding and reduce the rate of defects such as silver.
• the resin composition of the present invention can be used to obtain the desired molded product by methods such as injection molding, injection compression molding, injection blow molding, extrusion molding, or blow molding. Furthermore, the molded product of the present invention can be subjected to various surface treatments. Surface treatments referred to here are methods for forming a new layer on the surface of the resin molded product, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and methods used for ordinary thermoplastic resins can be applied. Specific examples of surface treatments include hard coating, water-repellent/oil-repellent coating, ultraviolet absorbing coating, infrared absorbing coating, and metallizing (vapor deposition, etc.).
• the polycarbonate resin composition of the present invention may contain various additives to impart various properties to the extent that the object of the present invention is not impaired.
• Additives that can be used include release agents, heat stabilizers, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants, heat shielding agents, fluorescent dyes (including fluorescent brighteners), pigments, light diffusing agents, reinforcing fillers, other resins and elastomers, etc.
• the weight ratio of the copolymer polycarbonate resin (component A) and the aromatic polycarbonate resin (component B) can be arbitrarily mixed within the range of 1:99 to 99:1.
• the range is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.
• the viscosity average molecular weight of the polycarbonate resin composition in the present invention is preferably in the range of 6,000 to 35,000, more preferably in the range of 8,000 to 32,000, still more preferably in the range of 10,000 to 30,000, particularly preferably in the range of 13,000 to 28,000, and most preferably in the range of 15,000 to 25,000. This is preferred because it has excellent heat resistance, scratch resistance, and impact resistance.
• the glass transition temperature (Tg) of the polycarbonate resin composition in the present invention is preferably single, and the temperature range is preferably 100 to 300 ° C., more preferably 120 to 250 ° C., even more preferably 130 to 220 ° C., and particularly preferably 140 to 200 ° C.
• the resin composition with the polycarbonate resin (B component) does not phase separate during extrusion or molding, and the resin composition does not become cloudy, and is preferable because it has good heat resistance and moldability.
• the glass transition temperature (Tg) is measured using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 ° C. / min. In the present invention, when the glass transition temperature (Tg) is single, only one inflection point indicating the glass transition temperature appears when the glass transition temperature is measured using DSC.
• the polycarbonate resin composition of the present invention preferably has a total light transmittance of 85% or more for a molded piece having a thickness of 2 mm. If the total light transmittance is within the above range, the range of use as an optical member is not limited, which is preferable.
• the polycarbonate resin composition in the present invention preferably has an indentation hardness of 150 to 400 (N/mm 2 ), more preferably 170 to 350 (N/mm 2 ), even more preferably 200 to 300 (N/mm 2 ), particularly preferably 215 to 290 (N/mm 2 ), and most preferably 225 to 280 (N/mm 2 ), as measured in accordance with ISO/TS 19278.
• the indentation hardness is within the above range, the molded article has excellent scratch resistance.
• pencil hardness which is a commonly used index for the scratch resistance of materials, is a discrete index with a range, so it is difficult to compare the hardness of materials with the same pencil hardness of "2H," for example. Therefore, by using indentation hardness, which allows for quantitative evaluation, as an index, it is possible to evaluate the degree of hardness even for materials with the same pencil hardness.
• the indentation hardness is measured based on ISO/TS 19278 by using a dynamic ultra-microhardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between the load and the indentation depth on the surface of the resin plate in real time.
• the pencil hardness of the polycarbonate resin composition in the present invention is preferably H or more, more preferably 2H or more, and even more preferably 3H or more.
• the pencil hardness is a hardness that does not leave a scratch mark when the polycarbonate resin is rubbed with a pencil having a specific pencil hardness, and it is preferable to use the pencil hardness used in the surface hardness test of the coating film that can be measured according to JIS K-5600 as an index.
• the pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.
• the polycarbonate resin composition of the present invention preferably has a notched Charpy impact strength of 1.5 kJ/ m2 or more, more preferably 2.0 kJ/ m2 or more, and even more preferably 3.0 kJ/ m2 or more, measured in accordance with ISO 179.
• a notched Charpy impact strength of 100 kJ/m2 or less provides sufficient functionality.
• DuPont impact test It is preferable that the polycarbonate resin composition of the present invention is not destroyed when a 1 kg weight is dropped from a height of 1 m using a DuPont impact deformation tester with a striking die (radius 6.35 mm) and a receiving die (inner diameter 15.2 mm, outer diameter 25.0 mm) and a parallel plate 50 mm in length and width and 2 mm in thickness placed between the receiving die and the striking die.
• Pencil hardness The obtained polycarbonate resin was press molded using a hot press molding machine (manufactured by Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disk-shaped resin plate with a thickness of about 3 mm.
• the press molding conditions were a mold temperature of 150 to 350 ° C., a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes).
• the obtained polycarbonate resin was press molded using a hot press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disk-shaped resin plate with a thickness of approximately 3 mm.
• the press molding conditions were a mold temperature of 150 to 350°C, a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes).
• Indentation hardness (Hit) is a measure of the resistance to semi-permanent deformation or damage. Indentation hardness is calculated by the following formula:
• Example A-2 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 114.80 parts by mass of ion-exchanged water and 35.15 parts by mass of a 25% aqueous sodium hydroxide solution, and 15.96 parts by mass of BNF, 9.07 parts by mass of BPC, and 0.050 parts by mass of hydrosulfite were dissolved as diol compounds, and then 90.35 parts by mass of methylene chloride was added, and 9.19 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. under stirring.
• the resin was then repeatedly washed with ion-exchanged water until the electrical conductivity of the aqueous phase became nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate.
• the methylene chloride solution thus obtained was then dropped into warm water maintained at 50 to 80°C, and the solvent was evaporated and removed to obtain a flaky solid.
• the obtained solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin.
• the obtained polycarbonate resin was used to carry out various evaluations using the methods described above, and the results are shown in Table 1.
• Example A-3 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 120.29 parts by mass of ion-exchanged water and 36.83 parts by mass of a 25% aqueous sodium hydroxide solution, and 16.73 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 8.46 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA; manufactured by Nippon Steel Chemical & Material Co., Ltd.) and 0.050 parts by mass of hydrosulfite were dissolved therein, and then 94.67 parts by mass of methylene chloride was added, and 9.63 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C.
• BNF 9,9-bis(6-hydroxy-2-naphthyl)fluorene
• BPA
• Example A-4 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 122.91 parts by mass of ion-exchanged water and 37.63 parts by mass of a 25% aqueous sodium hydroxide solution, and 6.84 parts by mass of BNF, 15.54 parts by mass of BPC, and 0.045 parts by mass of hydrosulfite were dissolved as diol compounds, and then 96.74 parts by mass of methylene chloride was added, and 9.84 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring.
• the resin was then repeatedly washed with ion-exchanged water until the electrical conductivity of the aqueous phase became nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate.
• the methylene chloride solution thus obtained was then dropped into warm water maintained at 50 to 80°C, and the solvent was evaporated and removed to obtain a flaky solid.
• the obtained solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin.
• the obtained polycarbonate resin was used to carry out various evaluations using the methods described above, and the results are shown in Table 1.
• Example A-5 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 110.92 parts by mass of ion-exchanged water and 33.96 parts by mass of a 25% aqueous sodium hydroxide solution, and 6.17 parts by mass of BNF, 7.01 parts by mass of BPC, 6.24 parts by mass of BPA, and 0.039 parts by mass of hydrosulfite were dissolved as diol compounds, and then 87.30 parts by mass of methylene chloride was added, and 8.88 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring.
• Example A-6 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 120.67 parts by mass of ion-exchanged water and 36.94 parts by mass of a 25% aqueous sodium hydroxide solution, and 3.36 parts by mass of BNF, 17.16 parts by mass of BPC, and 0.041 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 94.67 parts by mass of methylene chloride was added, and 9.66 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring.
• the resin was then repeatedly washed with ion-exchanged water until the electrical conductivity of the aqueous phase became nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate.
• the methylene chloride solution thus obtained was then dropped into warm water maintained at 50 to 80°C, and the solvent was evaporated and removed to obtain a flaky solid.
• the obtained solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin.
• the obtained polycarbonate resin was used to carry out various evaluations using the methods described above, and the results are shown in Table 1.
• thermometer a stirrer, and a reactor equipped with a reflux condenser were charged with 304.13 parts by mass of ion-exchanged water and 149.65 parts by mass of a 25% aqueous sodium hydroxide solution, and 3.36 parts by mass of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 69.61 parts by mass of BPC, and 0.162 parts by mass of hydrosulfite were dissolved therein.
• BCF 9,9-bis(4-hydroxy-3-methylphenyl)fluorene
• the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water.
• the washing liquid became neutral, hydrochloric acid was added.
• washing with ion-exchanged water was repeated until the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained.
• the obtained methylene chloride solution was dropped into warm water kept at 50 to 80°C, and the solvent was evaporated and removed, and a flaky solid was obtained. The obtained solid was dried at 120°C for 24 hours, and a white flaky polycarbonate resin was obtained.
• thermometer A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 80.81 parts by mass of ion-exchanged water and 35.91 parts by mass of a 25% aqueous sodium hydroxide solution, and 12.95 parts by mass of BPC and 2.91 parts by mass of BCHP-FL as diol compounds, and 0.032 parts by mass of hydrosulfite were dissolved therein. Then, 71.55 parts by mass of methylene chloride was added, and 7.50 parts by mass of phosgene was blown in over 70 minutes at 16 to 24 ° C. under stirring.
• the temperature was raised to 240° C. at a heating rate of 60° C./hr, and after the amount of phenol flowing out reached 70%, the pressure was reduced to 40 kPa/hr, and the polymerization reaction was carried out until a predetermined power was reached, and the resin was taken out of the flask after the reaction was completed.
• the properties of the obtained polycarbonate resin are shown in Table 2.
• the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water, and when the washing solution became neutral, it was washed with hydrochloric acid acid water. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was put into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a resin powder. After dehydration, it was dried at 100°C for 12 hours in a hot air circulation dryer to obtain a white powder-like polycarbonate resin.
• Water absorption rate (%) ⁇ (resin weight after water absorption ⁇ resin weight before water absorption)/resin weight before water absorption ⁇ 100
• the water absorption rate was measured over time, and the water absorption rate at which the equilibrium value was reached was determined as the saturated water absorption rate.
• Linear expansion coefficient 3 g of a sample was dissolved in methylene chloride, and then the methylene chloride was evaporated to obtain a cast film.
• thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Corp.) a sample having a length of 4 mm and a width of 20 mm was measured three times at a heating rate of 10°C/min and a cooling rate of 50°C/min to calculate the linear expansion coefficient in the measurement temperature range of 50 to 90°C, and the average value was calculated.
• Spectral Light Transmittance A polycarbonate resin powder was melt-kneaded at a temperature of 350 to 450°C using a twin-screw extruder (OMEGA30H manufactured by STEER) to obtain pellets.
• the pellets were dried at 140°C for 5 to 10 hours, and then molded at 350 to 450°C using an injection molding machine (FNX140 manufactured by Nissei Plastic Industrial Co., Ltd.) to obtain a molded product (thickness 1 mm).
• the spectral light transmittance was measured at a measurement wavelength range of 250 to 2500 nm at a thickness of 1 mm of the molded product using a UV-Vis-Infrared Spectrophotometer (V-770DS manufactured by JASCO Corporation).
• Example B-1 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 19176 parts by weight of ion-exchanged water and 7575 parts by weight of a 25% aqueous sodium hydroxide solution, and 4533 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2017 parts by weight of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisP-HTG; manufactured by Honshu Chemical Co., Ltd.) and 10.16 parts by weight of hydrosulfite were dissolved therein, and then 30184 parts by weight of methylene chloride was added, and 1500 parts by weight of phosgene was blown in over 80 minutes at 16 to
• the polycarbonate resin powder was melt-kneaded in a twin-screw extruder (OMEGA30H manufactured by STEER) at a cylinder and die temperature of 350 to 420°C to obtain pellets.
• the pellets were dried at 140°C for 10 hours and then molded at a cylinder temperature of 350 to 450°C using an injection molding machine (FNX140 manufactured by Nissei Plastic Industrial Co., Ltd.) to obtain a molded product (thickness 1 mm).
• the molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 3.
• Example B-2 The same procedure as in Example B-1 was carried out, except that the diol compounds were 3,466 parts by weight of BNF and 1,286 parts by weight of BisP-HTG. The evaluation results are shown in Table 3.
• Example B-3 The same procedure as in Example B-1 was carried out, except that the diol compounds were 2666 parts by weight of BNF, 1837 parts by weight of BisP-HTG, and 79.90 parts by weight of p-tert-butylphenol. The evaluation results are shown in Table 3.
• Example B-4 The same procedure as in Example B-1 was carried out, except that the diol compound was BNF4533 parts by weight and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (PPPBP; manufactured by Sakai Kogyo Co., Ltd.) was 697 parts by weight. The evaluation results are shown in Table 3.
• Example B-5 The same procedure as in Example B-1 was carried out, except that the diol compounds were 2666 parts by weight of BNF, 697 parts by weight of PPPBP, and 1284 parts by weight of BisP-HTG. The evaluation results are shown in Table 3.
• Example B-6 The same procedure as in Example B-1 was carried out, except that the diol compound was BNF4266 parts by weight and 2,2-bis(4-hydroxyphenyl)propane (BPA; manufactured by Nippon Steel Chemical & Material Co., Ltd.) was 535 parts by weight. The evaluation results are shown in Table 3.
• Example B-7 The same procedure as in Example B-1 was carried out, except that the diol compounds were BNF 3733 parts by weight and BPA 802 parts by weight. The evaluation results are shown in Table 3.
• Example B-8 The same procedure as in Example B-1 was carried out, except that 266 parts by weight of BNF and 3490 parts by weight of BisP-HTG were used as the diol compound.
• Example B-1 The same procedure as in Example B-1 was carried out except that 3674 parts by weight of BisP-HTG was used as the diol compound.
• the evaluation results are shown in Table 3.
• Comparative Example B-2 A thermometer, a stirrer, and a reactor equipped with a reflux condenser were charged with 12784 parts by weight of ion-exchanged water and 6628 parts by weight of a 25% aqueous sodium hydroxide solution, and 1738 parts by weight of BPA, 1286 parts by weight of BisP-HTG, and 6.05 parts by weight of hydrosulfite were dissolved as diol compounds, and then 15092 parts by weight of methylene chloride was added, and 1500 parts by weight of phosgene was blown in over 80 minutes at 16 to 24 ° C.
• the mixture was then repeatedly washed with ion-exchanged water until the electrical conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate.
• the methylene chloride solution was then dropped into warm water kept at 80°C, and the solvent was evaporated and removed to obtain a powder-like solid.
• the solid was dried at 120°C for 24 hours to obtain a white powder-like polycarbonate resin.
• the obtained powder was used to evaluate the composition ratio, viscosity average molecular weight, glass transition temperature, saturated water absorption, and linear expansion coefficient. The evaluation results are shown in Table 3.
• the polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG manufactured by Technobel Co., Ltd.] with both the cylinder and the die at 320°C to obtain pellets. A part of the obtained pellets was dried at 120°C for 12 hours or more, and then molded products (thickness 1 mm) were obtained using an injection molding machine (J-75E3 manufactured by Japan Steel Works) under conditions of a cylinder temperature of 320°C and a mold temperature of 100°C. The molded products were used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 3.
• Comparative Example B-3 A polycarbonate resin powder was obtained in the same manner as in Comparative Example B-2, except that 2140 parts by weight of BPA and 939 parts by weight of PPPBP were used as the diol compound. The composition ratio, viscosity average molecular weight, glass transition temperature, saturated water absorption, and linear expansion coefficient of the obtained powder were evaluated. The evaluation results are shown in Table 3.
• the polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG manufactured by Technobel Co., Ltd.] with both the cylinder and the die at 320°C to obtain pellets. A part of the obtained pellets was dried at 120°C for 12 hours or more, and then molded products (thickness 1 mm) were obtained using an injection molding machine (J-75E3 manufactured by Japan Steel Works) under conditions of a cylinder temperature of 320°C and a mold temperature of 100°C. The molded products were used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 3.
• Comparative Example B-4 A polycarbonate resin powder was obtained in the same manner as in Comparative Example B-2, except that 2675 parts by weight of BPA and 23.08 parts by weight of p-tert-butylphenol were used as the diol compound. The composition ratio, viscosity average molecular weight, glass transition temperature, saturated water absorption, and linear expansion coefficient of the obtained powder were evaluated. The evaluation results are shown in Table 3.
• Polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG, Technobel Corp.] with both the cylinder and die at 330°C to obtain pellets. A portion of the resulting pellets was dried at 120°C for more than 12 hours, and then molded into a molded product (thickness 1 mm) using an injection molding machine (J-75E3, Japan Steel Works) with a cylinder temperature of 340°C and a mold temperature of 120°C. The molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 3.
• the 2 mm thick part of the molded three-stage resin plate was measured with a haze meter 300A manufactured by Nippon Denshoku Industries Co., Ltd. and evaluated according to the following criteria. "Good”: Total light transmittance is 85% or more; “Poor”: Total light transmittance is less than 85% (4) Glass transition temperature (Tg) The measurement was carried out using a 2910 DSC manufactured by TA Instruments Japan, Inc., by heating about 10 mg of a sample at a temperature increase rate of 20° C./min. (5) Deflection temperature under load The deflection temperature under load of 0.45 MPa was measured in accordance with ISO 75.
• Indentation hardness (Hit) is a measure of the resistance to semi-permanent deformation or damage. Indentation hardness is calculated by the following formula:
• Notched Charpy Impact Value Pellets of the polycarbonate resin composition were dried at 90 to 120° C. for 12 hours, and then molded into bending test pieces at a cylinder temperature of 230 to 350° C. and a mold temperature of 80 to 120° C. using a JSWJ-75EIII manufactured by Japan Steel Works, Ltd. The notched Charpy impact test was measured in accordance with ISO179. (9) Weight drop resistance test: DuPont impact test A DuPont impact deformation test was carried out using a 2 mm thick part of the molded three-stage resin plate.
• Example C-2 ⁇ Production of polycarbonate resin composition> Except for the blend weight ratio of Resin-1/Resin-7 being 80:20, the same operations as in Example C-1 were carried out and the same evaluations were carried out. The evaluation results are shown in Table 4. The glass transition temperature of the obtained blend pellets was uniform.
• Example C-4 ⁇ Production of polycarbonate resin composition> Except for the blend weight ratio of Resin-1/Resin-7 being 70:30, the same operations as in Example C-1 were carried out and the same evaluations were carried out. The evaluation results are shown in Table 4. The glass transition temperature of the obtained blend pellets was uniform.
• Example C-5 ⁇ Production of polycarbonate resin composition> Except for the blend weight ratio of Resin-1/Resin-7 being 60:40, the same operations as in Example C-1 were carried out and the same evaluations were carried out. The evaluation results are shown in Table 4. The glass transition temperature of the obtained blend pellets was uniform.
• Example C-6 ⁇ Production of polycarbonate resin composition> Except for the blend weight ratio of Resin-1/Resin-7 being 50:50, the same operations as in Example C-1 were carried out and the same evaluations were carried out. The evaluation results are shown in Table 4. The glass transition temperature of the obtained blend pellets was uniform.
• Example C-7 ⁇ Production of polycarbonate resin composition> Except for the blend weight ratio of Resin-1/Resin-7 being 10:90, the same operations as in Example C-1 were carried out and the same evaluations were carried out. The evaluation results are shown in Table 4. The glass transition temperature of the obtained blend pellets was uniform.
• Example C-8 ⁇ Production of copolymer polycarbonate resin (component A)> A white powdery copolymer polycarbonate resin (resin-2) was obtained in the same manner as in Example C-1, except that 1911 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.), 2335 parts by weight of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (OCZ; manufactured by Honshu Chemical Co., Ltd.) and 8.49 parts by weight of hydrosulfite were used as the diol compound.
• BNF 9,9-bis(6-hydroxy-2-naphthyl)fluorene
• OCZ 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane
• hydrosulfite 8.49 parts by weight of hydrosulfite
• Example C-9 ⁇ Production of copolymer polycarbonate resin (component A)> A white powdery copolymer polycarbonate resin (Resin-3) was obtained by carrying out the same operation as in Example C-1, except that 2730 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.), 1551 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.) and 8.56 parts by weight of hydrosulfite were used as the diol compound.
• BNF 9,9-bis(6-hydroxy-2-naphthyl)fluorene
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• hydrosulfite 8.56 parts by weight of hydrosulfite
• Example C-10 ⁇ Production of copolymer polycarbonate resin (component A)> A white powdery copolymer polycarbonate resin (Resin-4) was obtained by carrying out the same operation as in Example C-1, except that 1092 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.), 2482 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.) and 7.15 parts by weight of hydrosulfite were used as the diol compound.
• BNF 9,9-bis(6-hydroxy-2-naphthyl)fluorene
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• hydrosulfite 7.15 parts by weight of hydrosulfite
• Example C-11 ⁇ Production of copolymer polycarbonate resin (component A)> A white powdery copolymer polycarbonate resin (Resin-5) was obtained by carrying out the same operation as in Example C-1, except that 546 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.), 2792 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.) and 6.68 parts by weight of hydrosulfite were used as the diol compound.
• BNF 9,9-bis(6-hydroxy-2-naphthyl)fluorene
• BPC 2,2-bis(4-hydroxy-3-methylphenyl)propane
• hydrosulfite hydrosulfite
• test pieces for various evaluations were molded using an injection molding machine (J-75E3 manufactured by Japan Steel Works, Ltd.) under conditions of a cylinder temperature of 230° C. and a mold temperature of 80° C.
• the evaluation results are shown in Table 4.
• the polycarbonate resin of the present invention has excellent scratch resistance and heat resistance, and therefore does not require coating treatment, and can be used for automobile interior parts such as interior lighting lamp lenses, display meter covers, meter dial plates, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, translucent parts, etc.
• the polycarbonate resin of the present invention has small dimensional changes due to heat or water absorption, and has excellent light transmittance and heat resistance, and therefore can be used for optical parts such as connectors and lenses used in high-temperature environments, and electric and electronic parts such as switches, sockets, sensor cases, and flexible films.

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