Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
• • 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
  • C08K5/43—Compounds containing sulfur bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/50—Phosphorus bound to carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/04—Antistatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

• the present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition imparted with good long-lasting antistatic properties and thermal stability.
• Polycarbonate resin is used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, office equipment parts, etc. due to its excellent properties such as mechanical strength, dimensional stability and flame retardancy.
• it since it has a large surface intrinsic resistance, when static electricity is generated on the surface of the molded body of polycarbonate resin, dust adheres and it is difficult to remove it, and there are problems such as malfunction when it is used as an electric device part. May cause. Therefore, many techniques related to a polycarbonate resin composition imparted with antistatic properties have been studied, and a method using a phosphonium sulfonic acid salt (see Patent Document 1) and a method using a surfactant such as a glycerin fatty acid ester. (See Patent Document 2) has been proposed.
• Patent Documents 1 and 2 have a drawback that they are inferior in sustainability such that the effect is significantly reduced by one washing with water.
• a method using a polyether ester amide has been proposed as a method for imparting continuous antistatic properties, but it is said that the heat stability during heat distortion and injection molding deteriorates. There is a drawback that the heat resistance (deflection temperature under load) is lowered, and it is difficult to achieve both good transparency.
• An object of the present invention is to provide a polycarbonate resin composition having excellent sustained antistatic properties and thermal stability and a molded product thereof.
• the present inventors have found that the above-mentioned problems can be solved by a polycarbonate resin composition containing a specific ion pair compound. That is, the present inventor has found that the above-mentioned problems can be achieved by the following polycarbonate resin composition and a molded product thereof.
• the ion pair compound It has a melting point of 80 ° C or less and The 5% weight loss temperature measured by TG-TDA (thermogravimetric differential thermal analysis) is 350 ° C.
• R 1 > R D- 20 (1) (in the formula, R 1 is The contact angle (°) of the water droplets of the resin composition having an ion pair compound content of 2 parts by weight, and RD is the contact angle (°) of the water droplets of the aromatic polycarbonate resin.)
• R 1 > R D- 15 (2) (In the formula, R 1 is the contact angle (°) of a water droplet of the resin composition having an ion pair compound content of 2 parts by weight, and R D is an aromatic. Contact angle (°) of water droplets of polycarbonate resin.) 3. 3.
• the resin composition according to the above item 1 or 2, wherein the ion pair compound is a compound represented by the following formula (I).
• R 1 represents an alkyl group having 6 to 12 carbon atoms
• R 2 represents an alkyl group having 10 to 20 carbon atoms
• M ⁇ represents an arbitrary anion.
• M ⁇ has the following formula (II).
• R 3 and R 4 are perfluoroalkyl groups having 1 to 4 carbon atoms, respectively, and R 3 and R 4 may be the same or different. ] 5.
• R 1 is a linear alkyl group having 6 to 8 carbon atoms
• R 2 is a linear alkyl group having 12 to 16 carbon atoms
• R 3 and R 4 are perfluoroalkyl groups having 1 to 4 carbon atoms, respectively.
• the above item 3 or 4 is characterized in that R 1 is a linear alkyl group having 6 carbon atoms
• R 2 is a linear alkyl group having 14 carbon atoms
• R 3 and R 4 are trifluoromethyl groups, respectively.
• the polycarbonate resin composition of the present invention is excellent in continuous antistatic property and thermal stability, it is useful in the information field such as a transport tray for semiconductor parts, which is highly required to suppress dust adsorption. It is also useful in the optical field such as lenses used in in-vehicle cameras, smartphones, etc., where transparency is further required.
• the resin material has a drawback that dust easily adheres to the resin material, which causes deterioration of image quality and sensing function.
• the resin material of the present invention can be expected to improve the above-mentioned defects. Further, it is also useful in the automobile field where continuous antistatic property is required (interior parts which require good appearance, etc.). Therefore, the industrial effect of the present invention is extremely large.
• the aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a divalent phenol with a carbonate precursor.
• the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
• dihydric phenol used here are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl).
• Propane commonly known as bisphenol A
• 2,2-bis (4-hydroxy-3-methylphenyl) propane 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-Phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
• 2,2-bis (4-hydroxyphenyl) Pentan 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane ,
• BPM 4,4'-(m-phenylenediisopropyridene) diphenol
• 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component.
• BCF 9,9-bis (4-hydroxyphenyl)
• BCF 9,9-bis (4-hydroxy-3-methylphenyl) fluorene
• these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate.
• the component A constituting the resin composition is the following copolymerized polycarbonates (1) to (3).
• BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate.
• BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate.
• BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and Bis in 100 mol% of the divalent phenol component constituting the polycarbonate.
• These special polycarbonates may be used alone or in admixture of two or more. Further, these can also be used by mixing them with a widely used bisphenol A type polycarbonate.
• Tg is 160 to 250 ° C., preferably 170 to 230 ° C., and the water absorption rate is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.14 to Polycarbonate which is 0.27%.
• the water absorption rate of polycarbonate is a value obtained by measuring the water content after immersing in water at 23 ° C. for 24 hours in accordance with ISO62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there.
• the Tg glass transition temperature
• DSC differential scanning calorimetry
• carbonate precursor carbonyl halide, carbonic acid diester or haloformate is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of divalent phenol.
• the polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid.
• a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol including an alicyclic type
• a polyester carbonate resin copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol may be a mixture of two or more of the obtained polycarbonate resins.
• the branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention.
• the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluoroglucolside, or 4,6-dimethyl-2,4,6-tris (4-hydroxidiphenyl) heptene-2, 2.
• the structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.
• branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 100 mol% in total including the structural units derived from divalent phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%.
• the ratio of such a branched structure can be calculated by 1 1 H-NMR measurement.
• the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
• the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid.
• Such as alicyclic dicarboxylic acid is preferably mentioned.
• the bifunctional alcohol an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.
• Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase ester exchange method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the aromatic polycarbonate resin of the present invention, are described in various documents and patents. This is a well-known method in publications.
• Melt volume rate of an aromatic polycarbonate resin in the present invention (300 ° C., 1.2 kg load) is not particularly limited, but is preferably 1 ⁇ 60cm 3 / 10min, more preferably 3 ⁇ 30cm 3 / 10min, more preferably is 5 ⁇ 20cm 3 / 10min.
• Resin composition melt volume rate is obtained from less than 1 cm 3 / 10min aromatic polycarbonate resin may be inferior in versatility in that poor flowability during injection molding.
• the polycarbonate resin melt volume rate is more than 60cm 3 / 10min, may not good mechanical properties are obtained.
• the melt volume rate is also called "MVR" and is measured according to ISO1133.
• a polycarbonate-polydiorganosiloxane copolymer resin can also be used as the aromatic polycarbonate resin (component A) of the present invention.
• the polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). It is preferably a polymer resin.
• R 1 and R 2 are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively.
• E and f are each an integer of 1 to 4
• W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2).
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon.
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and 6 to 12 carbon atoms, respectively.
• R 9 and R 10 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms and 1 to 10 carbon atoms, respectively.
• X is a divalent aliphatic group having 2 to 8 carbon atoms.
• Examples of the divalent phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and the like.
• 1,1-bis (4-hydroxyphenyl) -1-phenylethane 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-
• 1,1-bis (4-hydroxyphenyl) -1-phenylethane 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene, 1,4-bis ⁇ 2- (4-Hydroxyphenyl) propyl ⁇ benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-.
• BPZ 1,1-bis (4-hydroxyphenyl)
• Sulfonyldiphenol 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred.
• 2,2-bis (4-hydroxyphenyl) propane which has excellent strength and good durability, is most preferable.
• these may be used individually or in combination of 2 or more types.
• hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3) for example, the following compounds are preferably used.
• the hydroxyaryl-terminated polydiorganosiloxane (II) prescribes phenols having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol. It is easily produced by subjecting the terminal of a polysiloxane chain having the degree of polymerization of the above to a hydrosilylation reaction.
• (2-allylphenol) -terminal polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminal polydiorganosiloxane are preferable, and (2-allylphenol) -terminal polydimethylsiloxane and (2-methoxy-4) are particularly preferable.
• -Allylphenol) -terminated polydimethylsiloxane is preferred.
• the hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less.
• the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and low temperature impact property during high temperature molding. If the upper limit of such a suitable range is exceeded, the amount of outgas generated during high-temperature molding is large, and the low-temperature impact resistance may be inferior.
• the degree of polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is appropriately 10 to 300.
• the degree of polymerization of diorganosiloxane (p + q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of the suitable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and when the upper limit of the suitable range is exceeded, poor appearance appears.
• the content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50% by weight.
• the content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight.
• Above the lower limit of the suitable range impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, a stable appearance that is not easily affected by molding conditions can be easily obtained.
• the degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by 1 H-NMR measurement.
• hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.
• a comonomer other than the above divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be added in a range of 10% by weight or less based on the total weight of the copolymer. It can also be used together.
• a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by a reaction of a dihydric phenol (I) and a carbonic acid ester-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.
• the entire amount of divalent phenol (I) used in the method of the present invention may be an oligomer at a time, or a part thereof may be used as a post-added monomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-added monomer is added to allow the polycondensation reaction in the subsequent stage to proceed rapidly, and it is not necessary to add it when it is not necessary.
• the method of this oligomer-forming reaction is not particularly limited, but usually, a method performed in a solvent in the presence of an acid binder is preferable.
• the ratio of the carbonic acid ester-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Further, when a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably adopted.
• the acid binder for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof are used.
• the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of divalent phenol (I) used for forming the oligomer (usually 1 mol corresponds to 2 equivalents). ..
• a solvent inert to various reactions such as those used in the production of known polycarbonate may be used alone or as a mixed solvent.
• Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene.
• a halogenated hydrocarbon solvent such as methylene chloride is preferably used.
• the reaction pressure for oligomer formation is not particularly limited and may be normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure.
• the reaction temperature is selected from the range of ⁇ 20 to 50 ° C., and in many cases, heat is generated during polymerization, so water cooling or ice cooling is desirable.
• the reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours.
• the pH range of the oligomer-forming reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.
• the molecular weight distribution (Mw / Mn) is up to 3 or less while stirring the mixed solution.
• the highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are polycondensed. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
• R 9 and R 10 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and 1 to 10 carbon atoms, respectively.
• an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction.
• the acid binder for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof are used.
• the post-addition amount is two.
• Polycondensation by the interfacial polycondensation reaction between the oligomer of divalent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is performed by vigorously stirring the above mixture.
• a terminal terminator or a molecular weight modifier is usually used.
• the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol.
• the amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all the divalent phenolic compounds used, and it is naturally possible to use two or more kinds of compounds in combination. is there.
• a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to promote the polycondensation reaction.
• the reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
• the branching agent can be used in combination with the above divalent phenolic compound to obtain branched polycarbonate-polydiorganosiloxane.
• examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer resin include fluoroglucolcin, fluoroglucolside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl).
• the ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. It is mol%, more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%.
• the amount of the branched structure can be calculated by 1 1 H-NMR measurement.
• the reaction pressure can be reduced pressure, normal pressure, or pressurization, but usually, normal pressure or the self-pressure of the reaction system can be preferably used.
• the reaction temperature is selected from the range of ⁇ 20 to 50 ° C., and in many cases, heat is generated during polymerization, so water cooling or ice cooling is desirable. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be unconditionally specified, but it is usually carried out in 0.5 to 10 hours.
• the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to reduce the desired amount. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [ ⁇ SP / c].
• the obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by subjecting various post-treatments such as a known separation and purification method.
• the average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm.
• the average size is more preferably 1 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, impact resistance may not be stably exhibited. This provides a resin composition having excellent impact resistance and appearance.
• the average domain size of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention was evaluated by the small-angle X-ray scattering method (SAXS).
• SAXS small-angle X-ray scattering method
• the small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction occurring in a small-angle region within a scattering angle (2 ⁇ ) ⁇ 10 °. In this small-angle X-ray scattering method, if there are regions having different electron densities having a size of about 1 to 100 nm in a substance, diffuse scattering of X-rays is measured by the difference in electron densities.
• the particle size of the object to be measured is determined based on the scattering angle and the scattering intensity.
• a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain.
• the scattering intensity I at each scattering angle (2 ⁇ ) in the range where the scattering angle (2 ⁇ ) is less than 10 ° is measured, the small angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. From the tentative particle size and the tentative particle size distribution model, a simulation is performed using commercially available analysis software to obtain the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a matrix of polycarbonate polymers, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. it can.
• the average domain size means the number average of individual domain sizes.
• average domain size used in connection with the present invention is a measured value obtained by measuring a 1.0 mm thick portion of a three-stage plate produced by the method described in Examples by such a small angle X-ray scattering method. Shown. In addition, the analysis is performed using an isolated particle model that does not consider the interaction between particles (interference between particles).
• the ion pair compound used in the present invention is used as an antistatic agent, has a melting point of 80 ° C. or lower, a 5% weight loss temperature measured by TG-TDA of 350 ° C. or higher, and the following formula (1).
• R 1 > R D- 20 (1) In the formula, R 1 is the contact angle (°) of the water droplet of the resin composition having an ion pair compound content of 2 parts by weight, and R D is the contact angle (°) of the water droplet of the aromatic polycarbonate resin. Is.) To be satisfied.
• antistatic agents that are not ion-pair compounds include surfactants such as glycerin fatty acid esters, but resin compositions using these are inferior in sustained antistatic properties and thermal stability.
• resin compositions using these are inferior in sustained antistatic properties and thermal stability.
• polymer materials such as polyether as antistatic agents that are not ion-pair compounds, but resin compositions using these have the drawback of not being transparent and of being inferior in thermal stability and deflection temperature under load. There is.
• the melting point of the ion pair compound is 80 ° C. or lower. It is known that the resin composition becomes antistatic by adding an ion pair compound having a low melting point, particularly a liquid at room temperature, to the resin. The reason is that the ion pair compound having a low melting point has an organic compound moiety having a large size to some extent, so that the Coulomb force of positive and negative charges is weakened and the affinity with the matrix resin is increased. It is believed that it is appropriately dispersed in the resin composition and exhibits antistatic properties. In particular, when considering the addition to the polycarbonate resin, those having a melting point of 80 ° C. or lower are suitable for imparting good antistatic properties.
• an ion pair compound having a melting point of more than 80 ° C. has a strong Coulomb force or a small organic compound site and a low affinity with the resin, so that it is difficult to disperse in the aromatic polycarbonate resin and has good antistatic properties. Does not demonstrate.
• the melting point of the ion pair compound is preferably 30 ° C. or lower, more preferably 0 ° C. or lower.
• the 5% weight loss temperature measured by TG-TDA is 350 ° C. or higher.
• thermal decomposition of ion-to-compounds is likely to occur in an environment where the resin compound is exposed to high temperatures such as melt kneading and injection molding, and the compound generated by the thermal decomposition is the heat of the resin polymer. It also contributes to decomposition and causes problems such as a decrease in molecular weight.
• the treatment temperature in melt kneading or injection molding often reaches 300 to 350 ° C., so 350 ° C. or higher is appropriate.
• the 5% weight loss temperature measured by TG-TDA of the ion pair compound is preferably 355 ° C. or higher, and more preferably 360 ° C. or higher.
• the reason why the equation (1) should be satisfied will be described below.
• the more hydrophobic the ion-pair compound is the more the elution of the ion-pair compound into water when the resin composition containing the ion-pair compound comes into contact with water is suppressed, so that the continuous antistatic property is improved.
• the degree of hydrophobicity of the ion pair compound can be defined by the contact angle of the water droplet with respect to the resin composition to which the ion pair compound is added. If the formula (1) is not satisfied, it means that the ion-pair compound is more hydrophilic, so that when the resin composition comes into contact with water, the ion-pair compound elutes into water more and is sustained. Antistatic property cannot be ensured.
• R 1 is the contact angle (°) of the water droplet of the resin composition having an ion pair compound content of 2 parts by weight
• R D is the contact angle (°) of the water droplet of the thermoplastic resin. is there.
• the ion pair compound having a melting point of 80 ° C. or lower, a 5% weight loss temperature measured by TG-TDA of 350 ° C. or higher, and satisfying the formula (1) is a phosphonium salt satisfying the following formula (I). It is preferable to have.
• R 1 represents an alkyl group having 6 to 12 carbon atoms
• R 2 represents an alkyl group having 10 to 20 carbon atoms
• M ⁇ represents an arbitrary anion.
• M ⁇ in the above formula (I) is preferably the following formula (II).
• R 3 and R 4 each represent a perfluoroalkyl group having 1 to 4 carbon atoms, and R 3 and R 4 may be the same or different.
• R 1 is a linear alkyl group having 6 to 8 carbon atoms
• R 2 is a linear alkyl group having 12 to 16 carbon atoms
• R 3 and R 4 are carbon atoms 1 to 4, respectively. It is preferably a perfluoroalkyl group, in which R 1 is a linear alkyl group having 6 carbon atoms, R 2 is a linear alkyl group having 14 carbon atoms, and R 3 and R 4 are trifluoromethyl groups, respectively. preferable.
• the content of the B component is 0.3 to 5 parts by weight, preferably 0.4 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the A component. If the content of the B component is less than 0.3 parts by weight, good antistatic properties are not exhibited, and if it is more than 5 parts by weight, the resin viscosity decreases and the processability becomes unstable.
• the polycarbonate resin composition of the present invention preferably contains a phosphorus-based heat stabilizer to the extent that hydrolyzability is not promoted.
• a phosphorus-based heat stabilizer improve thermal stability during manufacturing or molding, and improve mechanical properties, hue, and molding stability.
• the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine.
• examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl.
• Phenylphosphite diisopropylmonophenylphosphenyl, monobutyldiphenylphosphenyl, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylpheny
• phosphite compound a compound that reacts with divalent phenols and has a cyclic structure can also be used.
• Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.
• Phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi.
• Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
• Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl.
• Examples include phosphine, triphenylphosphine, and diphenylbenzylphosphine.
• a particularly preferred tertiary phosphine is triphenylphosphine.
• the phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types.
• an alkyl phosphate compound typified by trimethyl phosphate is blended. It is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.
• the content of the phosphorus-based heat stabilizer is preferably 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, still more preferably 0.01, based on 100 parts by weight of the A component. ⁇ 0.2 parts by weight.
• Hindered phenol-based stabilizers can be added to the polycarbonate resin composition of the present invention. Such a formulation has an effect of suppressing deterioration of hue during molding processing and deterioration of hue during long-term use, for example.
• the hindered phenol-based stabilizer include ⁇ -tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl- ⁇ - (4'-hydroxy-3', 5'-di-tert-butylfel).
• the above hindered phenolic stabilizers can be used alone or in combination of two or more.
• the content of the hindered phenol-based stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the A component.
• Heat Stabilizers Other Than The Phosphorus Stabilizers and Hindered Phenol Stabilizers Other than the Phosphorus Stabilizers and Hindered Phenol Stabilizers can be added to the polycarbonate resin composition of the present invention.
• heat stabilizers for example, lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are preferably exemplified. Will be done. Details of such stabilizers are described in JP-A-7-233160.
• Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available.
• Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified.
• the content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the A component.
• Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated.
• the content of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the component A.
• An epoxy compound can be added to the polycarbonate resin composition of the present invention, if necessary. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically all compounds having an epoxy functional group can be applied.
• Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3', 4-'-epoxycyclohexylcarboxylate, and 1,2-epoxy-4-butanol of 2,2-bis (hydroxymethyl) -1-butanol.
• Examples thereof include a (2-oxylanyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate.
• the content of the epoxy compound is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, still more preferably 0.005, based on 100 parts by weight of the component A. ⁇ 0.1 parts by weight.
• a flame retardant can be added to the polycarbonate resin composition of the present invention.
• the formulation of such a compound brings about an improvement in flame retardancy, but other than that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity, and thermal stability is brought about.
• Such flame retardants include (i) organometallic salt-based flame retardants (for example, organosulfonic acid alkali (earth) metal salts, organoboric acid metal salt-based flame retardants, and organophosphorus metal salt-based flame retardants), ( ii) Organophosphorus flame retardant (for example, organic group-containing monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, etc.), (iii) Silicone flame retardant composed of silicone compound. , (Iv) fibrillated PTFE, among which organometallic salt-based flame retardants and organophosphorus flame retardants are preferred. These may be used alone or in combination of two.
• organometallic salt-based flame retardants for example, organosulfonic acid alkali (earth) metal salts, organoboric acid metal salt-based flame retardants, and organophosphorus metal salt-based flame retardants
• Organic metal salt-based flame retardant is an alkaline (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkaline (earth) metal salt of organic sulfonic acid. Is preferable.
• This organic sulfonic acid alkali (earth) metal salt includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal.
• metal salts of acids as well as metal salts of aromatic sulfonic acids with 7-50, preferably 7-40 carbon atoms and alkali metals or alkaline earth metals.
• alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium
• alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal.
• rubidium and cesium having a larger ionic radius are preferable when the demand for transparency is higher, but they are not versatile and difficult to purify, resulting in cost. It may be disadvantageous.
• metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy.
• the alkali metal in the sulfonic acid alkali metal salt can be used properly, but in all respects, the potassium sulfonic acid salt having an excellent balance of characteristics is the most suitable.
• Such a potassium salt and a sulfonic acid alkali metal salt composed of another alkali metal can also be used in combination.
• alkali metal salt of perfluoroalkyl sulfonic acid examples include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluoro.
• the number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.
• Fluoride ions (F-) are usually mixed in an alkali (earth) metal salt of perfluoroalkyl sulfonic acid composed of an alkali metal. Since the presence of such fluoride ions can be a factor for lowering the flame retardancy, it is preferable to reduce it as much as possible.
• the ratio of such fluoride ions can be measured by an ion chromatography method.
• the fluoride ion content is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Further, it is preferable that the production efficiency is 0.2 ppm or more.
• the perfluoroalkylsulfonic acid alkali (earth) metal salt having a reduced amount of fluoride ion is contained in a raw material for producing a fluorine-containing organic metal salt using a known production method.
• organic metal salt-based flame retardants are relatively soluble in water, so ion-exchanged water, especially water satisfying an electrical resistance value of 18 M ⁇ ⁇ cm or more, that is, an electrical conductivity of about 0.55 ⁇ S / cm or less is used. It is preferable to carry out the production by a step of melting at a temperature higher than room temperature, washing, and then cooling and recrystallizing.
• aromatic sulfonic acid alkali (earth) metal salt examples include, for example, diphenylsulfide-4,4'-disodium disulfonate, diphenylsulfide-4,4'-dipotassium disulfonate, potassium 5-sulfoisophthalate, and the like.
• aromatic sulfonic acid alkali (earth) metal salts potassium salts are particularly preferable.
• aromatic sulfonic acid alkali (earth) metal salts potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferable, and mixtures thereof (the former and the latter) are particularly preferable.
• the weight ratio of 15/85 to 30/70) is preferable.
• the organic metal salt other than the alkali (earth) metal salt of sulfonic acid include an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide.
• the alkali (earth) metal salt of the sulfate ester include an alkali (earth) metal salt of the sulfate ester of monovalent and / or polyhydric alcohols, such monovalent and / or polyhydric alcohols.
• Sulfate esters include methyl sulfate ester, ethyl sulfate ester, lauryl sulfate ester, hexadecyl sulfate ester, polyoxyethylene alkylphenyl ether sulfate ester, pentaerythritol mono, di, tri, tetrasulfate ester, and lauric acid monoglyceride sulfate. Examples thereof include an ester, a sulfate ester of palmitate monoglyceride, and a sulfate ester of stearate monoglyceride.
• Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, and N- ( Examples thereof include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide.
• the content of the organic metal salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0.01 part by weight with respect to 100 parts by weight of the component A. It is 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.
• Organophosphorus flame retardant As the organophosphorus flame retardant, an aryl phosphate compound and a phosphazene compound are preferably used. Since these organophosphorus flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved.
• the aryl phosphate compound various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one kind or two or more kinds of phosphate compounds represented by the following general formula (4) can be mentioned.
• M in the above formula represents a divalent organic group derived from divalent phenol
• Ar 1 , Ar 2 , Ar 3 , and Ar 4 are monovalent organic groups derived from monovalent phenol, respectively.
• A, b, c and d are independently 0 or 1
• m is an integer of 0 to 5
• m is the average value thereof. It represents a value of 0 to 5.
• the phosphate compound of the above formula may be a mixture of compounds having different m numbers, and in the case of such a mixture, the average m number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.
• Suitable specific examples of the dihydric phenol that induces M are hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, and bis (4).
• -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, with resorcinol, bisphenol A, and dihydroxydiphenyl being preferred.
• the monovalent phenol for inducing Ar 1 , Ar 2 , Ar 3 , and Ar 4 include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, which are preferable. Are phenol and 2,6-dimethylphenol.
• the monovalent phenol may be substituted with a halogen atom
• specific examples of the phosphate compound having a group derived from the monovalent phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples thereof include (2,4-dibromophenyl) phosphate and tris (4-bromophenyl) phosphate.
• phosphate compound not substituted with a halogen atom examples include monophosphate compounds such as triphenyl phosphate and tri (2,6-kisilyl) phosphate, and resorcinol bisdi (2,6-kisilyl) phosphate).
• a phosphate oligomer mainly composed of a phosphate oligomer, a phosphate oligomer mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and a phosphate ester oligomer mainly composed of bisphenol A bis (diphenyl phosphate) are suitable (here, if the main component is used).
• phosphazene compound various phosphazene compounds conventionally known as flame retardants can be used, but phosphazene compounds represented by the following general formulas (5) and (6) are preferable.
• X 1 , X 2 , X 3 , and X 4 represent organic groups that do not contain hydrogen, hydroxyl groups, amino groups, or halogen atoms, and r represents an integer of 3 to 10.
• examples of the halogen atom-free organic group represented by X 1 , X 2 , X 3 , and X 4 include an alkoxy group, a phenyl group, an amino group, and an allyl group.
• the cyclic phosphazene compound represented by the above formula (5) is preferable, and further, the cyclic phenoxyphosphazene in which X 1 and X 2 in the above formula (5) are phenoxy groups is particularly preferable.
• the content of the organic phosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and further preferably 5 to 20 parts by weight with respect to 100 parts by weight of the A component. If the blending amount of the organophosphorus flame retardant is less than 1 part by weight, the flame retardant effect is difficult to obtain, and if it exceeds 50 parts by weight, there is a problem that strand breakage or surging occurs during kneading extrusion and productivity decreases. May occur.
• Silicone-based flame retardant A silicone compound used as a silicone-based flame retardant improves flame retardancy by a chemical reaction during combustion.
• various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. Silicone compounds are highly flame-retardant, especially when a polycarbonate resin is used, by binding themselves during combustion or by binding to components derived from the resin to form a structure, or by a reduction reaction during structure formation. It is believed to give an effect.
• the preferably contains a group having high activity in such a reaction and more specifically, it contains a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group).
• the content ratio of such groups is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0. The range of 6 mol / 100 g is more preferable.
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.
• Q unit A tetrafunctional siloxane unit represented by SiO 2 .
• the structure of the silicone compound used in the silicone flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq and DnTpQq.
• the preferable structure of the silicone compound is MmDn, MmTp, MmDnTp, MmDnQq
• the more preferable structure is MmDn or MmDnTp.
• the coefficients m, n, p, and q in the formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the total of the coefficients in each formula is the average degree of polymerization of the silicone compound. ..
• the average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more suitable the range, the better the flame retardancy.
• the silicone compound containing a predetermined amount of aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained.
• the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. ..
• the silicone compound may be linear or have a branched structure.
• the organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
• Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and decyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group.
• aralkyl groups such as trill groups can be mentioned. More preferably, it is an alkyl group having 1 to 8 carbon atoms, an alkenyl group or an aryl group.
• the alkyl group an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.
• the silicone compound used as the silicone flame retardant preferably contains an aryl group.
• the silane compound and the siloxane compound as the organic surface treatment agent for the titanium dioxide pigment are clearly distinguished from the silicone-based flame retardant in the preferred embodiment in that a preferable effect can be obtained when the mixture does not contain an aryl group. ..
• the silicone compound used as a silicone-based flame retardant may contain a reactive group in addition to the Si—H group and the alkoxy group, and the reactive group includes, for example, an amino group, a carboxyl group, an epoxy group, and vinyl. Examples include groups, mercapto groups, and methacryloxy groups.
• the content of the silicone-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and further preferably 1 to 5 parts by weight with respect to 100 parts by weight of the component A.
• the fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer.
• the fibrillated PTFE has an extremely high molecular weight and tends to bond the PTFE to each other to form a fibrous form due to an external action such as a shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million.
• Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C., for example, as disclosed in Japanese Patent Application Laid-Open No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in such publication in the range of 10 7 to 10 13 poise, preferably in the range of 10 8 to 10 12 poise.
• the PTFE not only a solid form but also an aqueous dispersion form can be used. It is also possible to use such fibrillated PTFE in a mixed form with another resin in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties.
• a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell is also preferably used.
• Examples of commercially available products of such fibrillated PTFE include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Chemical Industry Co., Ltd.
• Examples of the fibrillated PTFE in the mixed form include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (A method described in Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957).
• the fibrillated PTFE is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, 20% by weight, based on 100% by weight of the mixture. Most preferably from% to 80% by weight.
• the content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, and 0.1 to 0 parts by weight, based on 100 parts by weight of the A component. 5 parts by weight is more preferable.
• the polycarbonate resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various designs.
• the dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridone dyes. Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes.
• the polycarbonate resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect that makes the best use of the emitted color.
• the fluorescent whitening agent is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white.
• examples thereof include benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds.
• Specific examples thereof include CI Fluorescent Fluorescent 219: 1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Chemical Industry Co., Ltd.'s "Hackor PSR".
• the fluorescent whitening agent has an action of absorbing the ultraviolet energy of light rays and radiating this energy to the visible portion.
• the content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the component A. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.
• the polycarbonate resin composition of the present invention can contain a compound having heat ray absorbing ability.
• Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, titanium oxide, lanthanum boride, cerium boride and tungsten boride.
• metal compounds having excellent near-infrared absorption ability such as metal boride-based and tungsten oxide-based near-infrared absorbers, and carbon fillers are preferably exemplified.
• a phthalocyanine-based near-infrared absorber for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available.
• the carbon filler include carbon black, graphite (including both natural and artificial) and fullerenes, and carbon black and graphite are preferable. These can be used alone or in combination of two or more.
• the content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and 0.001 to 0 parts by weight with respect to 100 parts by weight of the A component. .07 parts by weight is more preferred.
• the content of the metal oxide-based near-infrared ray absorber, the metal boride-based near-infrared ray absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the polycarbonate resin composition of the present invention.
• the range of 5 to 100 ppm is more preferable.
• the polycarbonate resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect.
• a light diffusing agent include high molecular weight fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof.
• Such polymer fine particles are fine particles already known as a light diffusing agent for polycarbonate resin. More preferably, acrylic crosslinked particles having a particle size of several ⁇ m and silicone crosslinked particles typified by polyorganosylsesquioxane are exemplified.
• the shape of the light diffusing agent include a spherical shape, a disk shape, a pillar shape, and an amorphous shape.
• Such a sphere includes a deformed one that does not have to be a perfect sphere, and such a pillar shape includes a cube.
• the preferred light diffusing agent is spherical, and the more uniform the particle size, the more preferable.
• the content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and further preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the component A. .. Two or more types of light diffusing agents can be used in combination.
• the polycarbonate resin composition of the present invention can be blended with a white pigment for high light reflection to impart a light reflection effect.
• a white pigment a titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable.
• the content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the A component. Two or more kinds of white pigments for high light reflection can be used in combination.
• the polycarbonate resin composition of the present invention can be blended with an ultraviolet absorber to impart weather resistance.
• an ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzine in the benzophenone system.
• an ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) benzotriazol and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazol in the benzotriazole system.
• -L 2- (2-Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2 '-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert- Butylphenyl) benzotriazol, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) Bentotriazol, 2-
• such ultraviolet absorbers include, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- ( 4,6-diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyl Oxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2) -Il) -5-butyloxyphenol and the like are exemplified.
• the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl.
• a compound that has become a phenyl group is exemplified.
• UV absorbers include, for example, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) and 2,2'-m-phenylenebis (3,1-benzoxazine-4-one). 3,1-benzoxazine-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like are exemplified.
• an ultraviolet absorber in the cyanoacrylate system, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [( Examples thereof include 2-cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.
• the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount such as an alkyl (meth) acrylate It may be a polymer-type ultraviolet absorber copolymerized with a body.
• a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. Ru.
• UV absorbers benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet-absorbing ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. Specific examples thereof include ChemiPro Kasei Co., Ltd. "Chemisorb 79" and BASF Japan Ltd. "Chinubin 234".
• the UV absorber may be used alone or in a mixture of two or more.
• the content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 1 part by weight, and particularly, with respect to 100 parts by weight of the A component. It is preferably 0.05 to 0.5 parts by weight.
• the polycarbonate resin composition of the present invention can be blended with various fillers known as reinforcing fillers other than the fibrous filler.
• various fillers known as reinforcing fillers other than the fibrous filler.
• examples of such a filler include various plate-shaped fillers and granular fillers.
• the plate-shaped filler is a filler having a plate-like shape (including those having irregularities on the surface and those having a curved plate).
• the granular filler is a filler having a shape other than these, including an indefinite shape.
• Plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers in which different materials such as metals and metal oxides are surface-coated on these fillers. Materials and the like are preferably exemplified.
• the particle size is preferably in the range of 0.1 to 300 ⁇ m. Such a particle size refers to a value based on the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 ⁇ m, and laser diffraction in the region of 10 to 50 ⁇ m.
• D50 median diameter
• the plate-shaped filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, and may be surface-treated, and may be olefin-based resin, styrene-based resin, acrylic-based resin, or polyester-based resin.
• an epoxy-based resin various resins such as a urethane-based resin, a higher fatty acid ester, or the like, or a granulated product which has been subjected to a focusing treatment or a compression treatment.
• (X) Other Resins and Elastomers In the polycarbonate resin composition of the present invention, other resins and elastomers are used instead of some of the resin components to exhibit the effects of the present invention as long as the effects of the present invention are not impaired. It can also be used in small proportions within the range.
• the blending amount of the other resin or elastomer is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the component composed of the A component and the B component.
• polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins.
• Phenolic resin epoxy resin and other resins.
• elastomer examples include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / styrene / butadiene), which is a core-shell type elastomer.
• examples thereof include rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.
• the polycarbonate resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents and the like.
• the polycarbonate resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. In producing such pellets, the above-mentioned various strengthening fillers and additives can also be blended.
• the reinforced polycarbonate resin composition of the present invention can usually produce various products by injection molding pellets produced as described above. Further, it is also possible to directly convert the resin melt-kneaded by the extruder into a sheet, a film, a modified extrusion molded product, a direct blow molded product, and an injection molded product without passing through pellets.
• injection molding not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, and insert molding, depending on the intended purpose.
• Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
• injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
• a cold runner method or a hot runner method can be selected for molding.
• the resin composition of the present invention can also be used in the form of various deformed extrusion-molded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc.
• the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.
• the resin molded product made of the polycarbonate resin composition of the present invention can usually be injection-molded with such pellets to obtain a molded product.
• injection molding it is possible to manufacture by a hot runner that enables runner-less as well as a usual cold runner type molding method.
• injection molding not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra). (Including those using a critical fluid), rapid heating and cooling mold molding, heat insulating mold molding and in-mold remelt molding, and a molding method consisting of a combination thereof can be used.
• the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
• the "part" is based on the weight standard. Based on the components and compounding amounts shown in Table 2, various compounding components are mixed using a tumbler and melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder (HYPER KTX30XHT manufactured by Kobe Steel) to obtain various pellets. It was.
• A-1 Teijin Limited Panlite L-1225WX (Viscosity average molecular weight: 19700)
• A-2 Teijin Limited Panlite L-1225WP (Viscosity average molecular weight: 22400)
• B component B-1: Trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide (manufactured by Kanto Chemical Co., Inc.)
• B-2 Comparison
• Methylethylbis trifluoromethylsulfonyl) imide (P12N111 manufactured by Mitsubishi Materials Corporation)
• B-3 Comparison): Potassium perfluorobutanesulfonate (Dainippon Ink and Chemicals Co., Ltd.
• B-4 Dodecylbenzene sulfonic acid tetrabutylphosphonium salt (DBS-P) (manufactured by Takemoto Oil & Fat Co., Ltd.) (C component)
• C-1 Phosphorus-based heat stabilizer (ADEKA STAB 2112 manufactured by ADEKA Corporation) (Other ingredients)
• D Phenolic heat stabilizer (ADEKA STAB A ⁇ -50 manufactured by ADEKA Corporation)
• E Fatty acid ester release agent (Rikemar SL900 manufactured by RIKEN Vitamin Co., Ltd.)
• F Surfactant-type antistatic agent (nonionic pair) (Poem DL-100 manufactured by RIKEN Vitamin Co., Ltd.)
• the obtained pellets were dried at 120 ° C. for 5 hours in a hot air circulation type dryer, and then a test piece for evaluation was molded using an injection molding machine (cylinder temperature 300 ° C., mold temperature 80 ° C.). The following evaluation was carried out.
• Antistatic property After wrapping a columnar weight with a surface resistivity of 500 g in a water-moistened Kim towel (manufactured by Nippon Paper Crecia Co., Ltd.), place it on the above flat plate test piece and slide it 10 times. The surface was wiped with water. The surface was then lightly wiped three times with a dry Kimwipe to wipe off water droplets. After that, 1. The surface resistivity was evaluated by the same method as above. 1. 1. The case where the surface resistivity of the same order as the initial value evaluated in 1 was shown was evaluated as ⁇ .
• Viscosity average molecular weight In injection molding, the viscosity average molecular weight (M 1 ) of the molded product formed after stopping the molding for 10 minutes and the viscosity average molecular weight (M 0 ) of the pellets are determined by the method described in the specification. It was measured. When M 0- M 1 ⁇ 2,000 was satisfied, it was evaluated as ⁇ , and when it was not satisfied, it was evaluated as x.
• a flat plate test obtained by injection-molding the contact angle (R 1 ) of water droplets of a resin composition containing 2 parts by weight of each ion pair compound with respect to 100 parts by weight of the polycarbonate resin under the above conditions using those resins. It was measured by dropping water droplets on the piece.
• Table 1 shows the melting points of B-1 to B-4, the 5% weight loss temperature, and the contact angle of water droplets.
• the contact angle (RD ) of the water droplets of the polycarbonate resin is 88 (°).
• Comparative Example 1 does not contain the B component and does not exhibit antistatic properties.
• Comparative Example 2 and Comparative Example 3 each contain an ion pair compound (B-2, B-3) having a melting point of more than 80 ° C., have a high surface resistivity before wiping with water, and do not exhibit antistatic properties. .. Comparative Example 4, 5% weight loss temperature is less than 350 ° C., R D -20 are contained R 1 is greater than the ion pair compound (B-4), poor sustained antistatic properties. Further, in injection molding, the viscosity average molecular weight of the molded product after retention is greatly reduced, and the thermal stability is inferior.
• Comparative Example 5 contains a surfactant-type antistatic agent (F), and is inferior in continuous antistatic property and thermal stability.
• F surfactant-type antistatic agent
• Comparative Example 6 since the content of the B component exceeded 5 parts by weight, the measurement became unstable due to the influence of the decrease in the viscosity of the pellets, and a molded product suitable for evaluation could not be obtained.

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• 2020
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