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
  • C08G64/18—Block or graft polymers
  • C08G64/186—Block or graft polymers containing polysiloxane sequences
• • 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
  • C08G64/18—Block or graft polymers
  • C08G64/183—Block or graft polymers containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
  • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • 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
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms

Definitions

• the present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate resin composition, and a molded article.
• Polycarbonate resin is an engineering plastic with excellent transparency and mechanical properties, and extremely high impact resistance.
• Polycarbonate-polyorganosiloxane copolymers which are polycarbonate and polyorganosiloxane copolymerized, are known to have excellent low-temperature impact resistance and chemical resistance while maintaining high transparency.
• polycarbonate resins are produced by directly reacting an aromatic dihydroxy compound with phosgene (interfacial polycondensation method) or by transesterifying an aromatic dihydroxy compound and a carbonic acid diester in a molten state (melt polycondensation method). legal) is known.
• Patent Document 1 discloses a method for producing a polycarbonate-polyorganosiloxane copolymer by an interfacial polycondensation method, in which a diaryl diol compound such as bisphenol and phosgene are reacted in the presence of an organic solvent to form a reactive chloroformate. Simultaneously or sequentially with the production of the polycarbonate oligomer, the polycarbonate oligomer, bisphenols, and a polyorganosiloxane having a hydroxyl group-containing aryl group at both ends are added to a methylene chloride/water medium. Disclosed is a method of manufacturing by contacting in a medium.
• a homocoupled product in which the same raw material components are bonded to each other, or unreacted raw material components may be generated because some raw materials do not participate in the polymerization reaction. Since these components exist in the polymer without being uniformly incorporated into the polymer main chain, the transparency and mechanical properties of the polymer are significantly reduced. In the above interfacial polymerization method, such problems rarely occur, and a polycarbonate-polyorganosiloxane copolymer having excellent transparency and mechanical properties can be obtained.
• the interfacial polymerization method requires the use of highly toxic phosgene as a carbonate source.
• phosgene as a carbonate source.
• methylene chloride as a solvent in the polymerization reaction system, which has a large environmental impact, and its removal requires a large degassing device and a large amount of energy, which is economically disadvantageous.
• a method for producing a polycarbonate-polyorganosiloxane copolymer using a melt polymerization method can avoid such problems.
• Patent Documents 2 to 4 disclose a polyorganosiloxane block (A) containing a specific structural unit such as a polyol structure, which can be produced by a melt polymerization method and has high transparency. -1) and a specific polycarbonate block (A-2), a polycarbonate-polyorganosiloxane copolymer is disclosed.
• Patent Documents 2 to 4 disclose a method for producing a polycarbonate-polyorganosiloxane copolymer by a melt polymerization method, but there is room for improvement in fluidity, impact strength, tensile strength, appearance of injection molded products, etc. there were.
• An object of the present invention is to obtain a polycarbonate-polyorganosiloxane copolymer that has excellent fluidity and a molded product that has excellent impact resistance, tensile elongation, and appearance.
• the present invention includes the following. ⁇ 1> A polyorganosiloxane-containing block (A-1) containing a structural unit represented by the following general formula (1), A polycarbonate-polyorganosiloxane copolymer (A) comprising a polycarbonate block (A-2) containing repeating structural units represented by the following general formula (2), The content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less, A polycarbonate-polyorganosiloxane copolymer in which the ratio of the average value of n b to the average value of n a [(average value of n b )/(average value of n a )] is 0.2 or more and 0.4 or less Combined.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or Indicates an alkylaryl group having 7 to 22 carbon atoms.
• R 5 and R 6 each independently represent an alkylene group having 1 to 3 carbon atoms, and these groups include -O-, -COO-, -CO in at least one of the main chain and side chain. It may contain at least one group selected from the group consisting of -, -S-, -NH-, and -NR 111 -.
• a plurality of R 7 and R 8 may be the same or different, and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these The group has at least one group selected from the group consisting of -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - in at least one of the main chain and the side chain. may include.
• R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• z 1 , z 2 , u 1 and u 2 each represent 0 or 1.
• n a represents an integer of 2 to 500
• n b each independently represents an integer of 2 to 200.
• R 10 is a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. These groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
• R 1 to R 8 , z 1 , z 2 , u 1 , u 2 , n a , and n b represent the same meanings as above. When a plurality of these exist, they may be the same or different.
• ⁇ represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid.
• the polycarbonate block (A-2) consisting of repeating structural units represented by the general formula (2) above includes the structural units represented by the following general formula (111), ⁇ 1> to ⁇ 4 above
• R 55 and R 56 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon It represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 -, -O- or -CO-.
• s and t each independently represent an integer of 0 to 4.
• R 1 to R 4 each represent a methyl group.
• R 5 and R 6 each represent a trimethylene group (-(CH 2 ) 3 -). Polyorganosiloxane copolymer.
• R 7 and R 8 are each a dimethylene group (-(CH 2 ) 2 -), a methyl-substituted dimethylene group (-CH 2 CH(CH 3 )- or -CH(CH 3 )CH 2 -), trimethylene group (-(CH 2 ) 3 -), or tetramethylene group (-(CH 2 ) 4 -) according to any one of ⁇ 1> to ⁇ 7> above.
• Polycarbonate-polyorganosiloxane copolymer are each a dimethylene group (-(CH 2 ) 2 -), a methyl-substituted dimethylene group (-CH 2 CH(CH 3 )- or -CH(CH 3 )CH 2 -), trimethylene group (-(CH 2 ) 3 -), or tetramethylene group (-(CH 2 ) 4 -) according to any one of ⁇ 1> to ⁇ 7> above.
• a polyorganosiloxane structure (A- The polycarbonate-polyorganosiloxane copolymer according to any one of ⁇ 1> to ⁇ 8> above, wherein the content of 3) is 0.1% by mass or more and 30% by mass or less.
• R 1 to R 2 represent the same meanings as above.]
• ⁇ 10> The polycarbonate-polyorganosiloxane copolymer according to any one of ⁇ 1> to ⁇ 9> above, which has a viscosity average molecular weight (Mv) of 15,000 or more and 30,000 or less.
• Mv viscosity average molecular weight
• ⁇ 11> The polycarbonate-polyorganosiloxane copolymer according to any one of ⁇ 1> to ⁇ 10> above, which is obtained by a melt polymerization method.
• ⁇ 12> The polycarbonate-polyorganosiloxane copolymer according to any one of ⁇ 1> to ⁇ 11> above, which is obtained using the diol monomer (a1).
• a polycarbonate resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of ⁇ 1> to ⁇ 12> above.
• the polycarbonate-polyorganosiloxane copolymer (A) of the present invention comprises a polyorganosiloxane-containing block (A-1) containing a structural unit represented by the following general formula (1), A polycarbonate block (A-2) containing repeating structural units represented by the following general formula (2),
• the content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less,
• the ratio of the average value of nb to the average value of na [(average value of nb )/(average value of na )] is 0.2 or more and 0.4 or less.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or Indicates an alkylaryl group having 7 to 22 carbon atoms.
• R 5 and R 6 each independently represent an alkylene group having 1 to 3 carbon atoms, and these groups include -O-, -COO-, -CO in at least one of the main chain and side chain. It may contain at least one group selected from the group consisting of -, -S-, -NH-, and -NR 111 -.
• a plurality of R 7 and R 8 may be the same or different, and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these The group has at least one group selected from the group consisting of -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - in at least one of the main chain and the side chain. may include.
• R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• z 1 , z 2 , u 1 and u 2 each represent 0 or 1.
• n a represents an integer of 2 to 500
• n b each independently represents an integer of 2 to 200.
• R 10 is a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. These groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. ]
• the polyorganosiloxane block (A-1) is any of the above general formula (1), the following general formula (1-2), or the following general formula (1-3). It is preferable that it is a structural unit represented by the following.
• the polycarbonate-polyorganosiloxane copolymer (A) can contain multiple types of polyorganosiloxane blocks (A-1).
• the polyorganosiloxane block (A-1) is more preferably a structural unit represented by the above general formula (1).
• R 1 to R 8 , z 1 , z 2 , u 1 , u 2 , n a , and n b represent the same meanings as above. When a plurality of these exist, they may be the same or different.
• ⁇ represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid.
• the halogen atom represented by R 1 to R 4 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group having 1 to 10 carbon atoms represented by R 1 to R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Note that the term "various" in this specification includes linear and all branched chains, and the same applies hereinafter.
• Examples of the alkoxy group having 1 to 10 carbon atoms represented by R 1 to R 4 include alkoxy groups in which the alkyl group moiety is the same as the alkyl group described above.
• Examples of the aryl group having 6 to 12 carbon atoms represented by R 1 to R 4 include a phenyl group and a naphthyl group.
• the alkyl arylene group having 7 to 22 carbon atoms represented by R 1 to R 4 has the same alkyl group as the alkyl group, and the arylene group is a divalent group obtained by removing one hydrogen atom from the aryl group. Certain alkylarylene groups are mentioned.
• R 1 to R 4 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, More preferably each is an alkyl group having 1 to 6 carbon atoms, and even more preferably each is a methyl group.
• Examples of the alkylene group having 1 to 3 carbon atoms represented by R 5 and R 6 include a methylene group, a dimethylene group, a trimethylene group, and a methyl-substituted dimethylene group.
• the arylene group having 6 to 20 carbon atoms represented by R 7 and R 8 includes a phenylene group and a naphthylene group.
• Examples of the alkylene group having 1 to 10 carbon atoms represented by R 7 and R 8 include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and various butylene groups.
• the various butylene groups are preferably tetramethylene groups.
• Examples of the alkylarylene group represented by R 7 and R 8 include an alkylarylene group in which the alkyl group part is the same as the above-mentioned alkylene group, and the arylene group part is the same as the above-mentioned arylene group.
• R 5 , R 6 , R 7 , and R 8 have -O-, -COO-, -OCO-, -CO-, -S-, -NH in at least one of the main chain and side chain.
• R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms represented by R 111 include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.
• Examples of the aryl group having 6 to 10 carbon atoms represented by R 111 include a phenyl group and a naphthyl group.
• R 5 and R 6 are each preferably a methylene group (-(CH 2 )-), a dimethylene group (-(CH 2 ) 2 -), or a trimethylene group (-(CH 2 ) 3 -), more preferably each It is a trimethylene group (-(CH 2 ) 3 -).
• R 7 and R 8 are each preferably an alkylene group having 1 to 10 carbon atoms, more preferably each being an alkylene group having 1 to 5 carbon atoms, and even more preferably each being a dimethylene group (-(CH 2 ) 2 -) or methyl.
• Substituted dimethylene group (-CH 2 CH(CH 3 )- or -CH(CH 3 )CH 2 -), trimethylene group, or tetramethylene group (-(CH 2 ) 4 -), each more preferably a dimethylene group .
• z 1 , z 2 , u 1 and u 2 are each 0 or 1. It is preferable that z 1 and z 2 are each 1, and it is more preferable that z 1 and z 2 are both 1. It is preferable that u 1 and u 2 are each 1, and it is more preferable that both u 1 and u 2 are 1.
• R 1 to R 4 are all methyl groups
• R 5 and R 6 are both trimethylene groups
• R 7 and R 8 are both dimethylene groups
• z 1 and z A polyorganosiloxane block in which both 2 is 1 and u 1 and u 2 are both 1 is preferred.
• n a represents the chain length of the polyorganosiloxane structure in general formula (1).
• n a is an integer of 2 or more and 500 or less, preferably an integer of 10 or more and 90 or less, more preferably an integer of 20 or more and 70 or less, still more preferably 30 or more. It is an integer of 60 or less, more preferably an integer of 35 or more and 50 or less.
• the average value of n a that is, the average chain length of the polyorganosiloxane structure in general formula (1) is 2 or more and 500 or less, preferably 10 or more and 90 or less, more preferably 20 or more and 70 or less, and even more preferably 30 or more.
• the average chain length of the polyorganosiloxane structure in general formula (1) is within the above range, a copolymer whose molded product has excellent impact resistance, tensile elongation, and appearance can be obtained.
• the repeating number of the -SiR 1 R 2 -O- structure in general formula (1) is n a -1.
• the average chain length of the polyorganosiloxane structure in general formula (1) is calculated by nuclear magnetic resonance (NMR) measurement.
• n b represents the number of repeats of the -(O) Z 1 -R 7 - structure and the -R 8 -(O) Z 2 - structure in general formula (1).
• n b is an integer from 2 to 200, preferably from 3 to 40, more preferably from 7 to 30, even more preferably from 10 to 25, even more preferably from 10 to 20. is an integer.
• the average value of n b that is, the -(O) Z 1 -R 7 - structure and -R 8 -(O) Z 2 - structure in general formula (1)
• the average number of repetitions is 2 or more and 200 or less, preferably 3 or more and 40 or less, more preferably 7 or more and 30 or less, still more preferably 10 or more and 25 or less, and still more preferably 10 or more and 20 or less.
• the above range is preferable because of the ease of obtaining raw materials for producing the polycarbonate-polyorganosiloxane copolymer (A).
• n b is 10 or more because it is possible to further improve the balance between the mechanical strength and mold releasability of the molded article of the polycarbonate-polyorganosiloxane copolymer (A) obtained, and It is more preferable that b is 100 or less because the viscosity and melting point of the polyorganosiloxane at the time of production are in a suitable range, and the handleability is further improved. It is more preferable that n b is 50 or less because the effect of improving physical properties due to the polycarbonate-polyorganosiloxane copolymer (A) containing the polyorganosiloxane block is further improved.
• the average number of repeats of the -(O) Z 1 -R 7 - structure and -R 8 -(O) Z 2 - structure in general formula (1) is calculated by nuclear magnetic resonance (NMR) measurement.
• the ratio of the average value of n b to the average value of n a [(average value of n b )/(average value of n a )] is 0.2 or more and 0. 4 or less.
• the ratio of the average value of n b to the average value of n a is within the above range, a copolymer having excellent fluidity and a molded article having excellent impact resistance, tensile elongation, and appearance can be obtained.
• the ratio of the average value of n b to the average value of na [(average value of n b )/(average value of na )] is 0.2.
• the polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the following general formula (3) contained in the polyorganosiloxane-containing block (A-1) represented by the above general formula (1) is a polycarbonate - It is known that physical properties such as impact resistance can be imparted to the polyorganosiloxane copolymer (A). However, since the polyorganosiloxane structure (A-3) has a low polarity, it has insufficient compatibility with the polycarbonate block (A-2), which has a highly polar structure.
• the polyorganosiloxane structure (A-3) will separate from the polycarbonate block (A-2) to form a phase-separated structure, resulting in insufficient physical properties such as tensile elongation and appearance of the molded product. It is thought that there may be cases where this occurs.
• the -(O) Z 1 -R 7 - structure and -R 8 -(O) Z 2 - structure contained in the polyorganosiloxane-containing block (A-1) represented by the above general formula (1) have polarity. Although these structures have high compatibility with the highly polar polycarbonate block (A-2), -(O) Z 1 -R 7 - structure and -R 8 -(O) Z 2 - Since the structure is relatively flexible, its strength is low, and if its content is too large, the physical properties such as impact resistance of the molded product of polycarbonate-polyorganosiloxane copolymer (A) will be insufficient. It is thought that there is.
• the average chain length of the polyorganosiloxane structure contained in the polycarbonate-polyorganosiloxane copolymer (A) of the present invention, the -(O) Z 1 -R 7 - structure and the -R 8 -(O) Z 2 - By setting the ratio of the average number of repeats of the structure within a predetermined range, a polycarbonate-polyorganosiloxane copolymer (A) with excellent fluidity and a molded product with excellent impact resistance, tensile elongation, and appearance can be obtained. It is thought that it will be possible.
• the polycarbonate-polyorganosiloxane copolymer (A) of the present invention has a ratio of the average value of nb to the average value of na [(average value of nb )/(average value of na )] of 0.2.
• the above is the content of the highly polar -(O) Z 1 -R 7 - structure and -R 8 -(O) Z 2 - structure relative to the content of the low polar polyorganosiloxane structure (A-3). It is considered that the polyorganosiloxane structure (A-3) and the polycarbonate block (A-2) are sufficiently large and compatible with each other.
• the polyorganosiloxane-containing block (A-1) does not form phase separation in the resin structure of the polycarbonate-polyorganosiloxane copolymer (A), and has excellent physical properties such as tensile elongation and color tone of the molded product. It is believed that this appearance can be achieved. Further, the polycarbonate-polyorganosiloxane copolymer (A) of the present invention has a ratio of the average value of n b to the average value of na [(average value of n b ) /(average value of n a )] of 0.
• the polycarbonate-polyorganosiloxane copolymer (A) can provide molded articles with excellent physical properties such as impact resistance.
• the ratio of the average value of nb to the average value of na [(average value of nb )/(average value of na )] is preferably 0.22 or more and 0.35 or less, more preferably 0.24 or more. It is 0.30 or less.
• Examples of the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by R 10 in the above general formula (2) include ethylene group, n-propylene group, isopropylene group, n-butylene group, and isobutylene group.
• n-pentylene group n-hexylene group, n-heptylene group, n-octylene group, 2-ethylhexylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, n- Examples include tridecylene group, n-tetradecylene group, n-pentadecylene group, n-hexadecylene group, n-heptadecylene group, and n-octadecylene group.
• these groups may be substituted with a substituent, and may also contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
• Examples of the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by R 10 in the above general formula (2) include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, and a cyclodecylene group.
• Examples include a tetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, and a tricyclodecylene group.
• these groups may be substituted with a substituent, and may also contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
• the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 10 in the above general formula (2) includes 2,2-bis(4-hydroxyphenyl)propane (also referred to as bisphenol A), 2 , 2-bis(4-hydroxy-3-methylphenyl)propane (also called bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (also called bisphenol Z), 1,1-bis(4 -Hydroxyphenyl)-3-methylcyclohexane (also referred to as bisphenol 3MZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (also referred to as bisphenol HTG), 1,1-bis Mention may be made of divalent aromatic hydrocarbon radicals derived from (4-hydroxyphenyl)cyclododecene, hydroquinone, resorcinol and catechol. However, these groups may be substituted with a substituent, and may also contain at least one atom selected from the group consist
• the polycarbonate block (A-2) consisting of repeating structural units represented by general formula (2) above preferably contains repeating structural units represented by general formula (111).
• R 55 and R 56 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cyclo group having 5 to 15 carbon atoms;
• s and t each independently represent an integer of 0 to 4.
• Examples of the halogen atom represented by R 55 and R 56 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkyl group having 1 to 6 carbon atoms represented by R 55 and R 56 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.
• the alkoxy group having 1 to 6 carbon atoms represented by R 55 and R 56 includes an alkoxy group in which the alkyl group moiety is the same as the alkyl group described above.
• Examples of the alkylene group having 1 to 8 carbon atoms represented by X include a methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, and the like, with an alkylene group having 1 to 5 carbon atoms being preferred.
• Examples of the alkylidene group having 2 to 8 carbon atoms represented by X include ethylidene group and isopropylidene group.
• Examples of the cycloalkylene group having 5 to 15 carbon atoms represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, with a cycloalkylene group having 5 to 10 carbon atoms being preferred.
• Examples of the arylene group having 6 to 20 carbon atoms represented by X include a phenylene group, a naphthylene group, and a biphenylene group.
• Examples of the cycloalkylidene group having 5 to 15 carbon atoms represented by X include a cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, and 2-adamantylidene group; A cycloalkylidene group is preferred, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferred.
• Examples of the arylalkylene group having 7 to 15 carbon atoms represented by Examples include arylalkylene groups, which are the same as alkylene.
• As the aryl alkylidene group having 7 to 15 carbon atoms represented by Examples include arylalkylidene groups which are the same as alkylidene.
• s and t each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.
• X represents a single bond or an alkylene group having 1 to 8 carbon atoms
• s and t are 0, and X represents an alkylidene group
• s and t are 0, and X represents an isopropylidene group.
• the polycarbonate block (A-2) consisting of repeating structural units represented by the above general formula (2) can contain structural units other than the structural units represented by the general formula (111). Specifically, the polycarbonate block (A-2) consisting of repeating structural units represented by the general formula (2) above can further include a structural unit represented by the general formula (112).
• R 100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and the divalent aliphatic hydrocarbon group has at least one selected from the group consisting of a branched structure and a cyclic structure. or at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
• the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by R 100 includes an alkylene group having 2 to 40 carbon atoms, a cycloalkylene group having 4 to 40 carbon atoms, and an oxygen or nitrogen group having 4 to 40 carbon atoms.
• Examples thereof include divalent saturated heterocyclic groups.
• the alkylene group preferably has 2 to 18 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 3 to 6 carbon atoms.
• the number of carbon atoms in the cycloalkylene group is preferably 4 to 20, more preferably 5 to 20.
• the oxygen- or nitrogen-containing divalent saturated heterocyclic group preferably has 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms.
• these groups may contain at least one atom selected from the group consisting of a branched structure and a cyclic structure, and may also contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. May include.
• alkylene group having 2 to 40 carbon atoms examples include ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group.
• Examples of the cycloalkylene group having 4 to 40 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, and a bicyclodecylene group. , and tricyclodecylene group.
• Examples of the oxygen- or nitrogen-containing divalent heterocyclic group having 4 to 40 carbon atoms include those containing an oxygen or nitrogen atom in the cycloalkylene skeleton.
• structural unit represented by the above general formula (112) include structural units represented by the following general formulas (ai) to (a-xiii).
• the polycarbonate block (A-2) consisting of repeating structural units represented by general formula (2) is composed of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methyl phenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3, 5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecene, isosorbide, cyclohexane-1,4-dimethanol, tricyclodecanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxy) derived from at least one compound selected from the group consisting of (ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanedio
• the polycarbonate block (A-2) preferably contains a structural unit represented by general formula (2) as a main component.
• the polycarbonate block (A-2) contains the structural unit represented by the general formula (2), preferably at least 50% by mass, more preferably at least 80% by mass, based on the polyorganosiloxane-containing block (A-1). More preferably, it contains 90% by mass or more, still more preferably 98% by mass or more. More preferably, the polycarbonate block (A-2) consists only of repeating structural units represented by general formula (2). Among these, it is particularly preferable to consist only of repeating structural units represented by general formula (111).
• they are bonded via.
• the polyorganosiloxane block (A-1) is a structural unit represented by the above general formula (1)
• the structural units represented by the above general formula (1) are adjacent to each other via a carbonate linkage. It is directly bonded to the polycarbonate block (A-2).
• the structure represented by a chemical formula may have optical isomers, stereoisomers, etc. due to the presence of an asymmetric center. In this case all isomers and mixtures thereof are included.
• the structural unit represented by the above general formula (a-iii) preferably includes a structural unit represented by the following general formula (a-iii'), more preferably the following general formula (a-iii'). Consists only of structural units represented by .
• the content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is 2% by mass or more and 30% by mass or less. When the content of the polyorganosiloxane-containing block (A-1) is within the above range, a copolymer having excellent fluidity and excellent impact resistance of a molded article can be obtained.
• the content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2.5% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass.
• the content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) refers to the polycarbonate block (A-2), the general formula (3)
• R Y is R 7 or R 8 .
• z 0 is z 2 ;
• R Y is R 7 , z 0 is z 1 .
• R 7 , R 8 , z 1 and z 2 have the same meanings as above.
• a polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the above general formula (3) contained in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)
• the content is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and still more preferably 1.0% by mass or more and 10% by mass or less.
• a copolymer having better impact resistance of a molded article can be obtained.
• polyorganosiloxane consisting of repeating structural units represented by the above general formula (3) contained in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)
• Constent of structure (A-3) means polycarbonate block (A-2), the structural unit represented by the general formula (3), the structural unit represented by the general formula (Y), and if necessary Accordingly, it is the percentage of the total mass of the structural units represented by the general formula (3) with respect to the total mass of the terminal structures derived from the terminal capping agent described below contained in the polycarbonate-polyorganosiloxane copolymer (A).
• the content of the polycarbonate block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, even more preferably is 90% by weight or more, and preferably 99.9% by weight or less, more preferably 99.5% by weight or less, even more preferably 99.0% by weight or less, even more preferably 97.0% by weight or less.
• the viscosity average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 15,000 or more and 30,000 or less, more preferably 17,000 or more and 27,000 or less, and even more preferably 18,000 or more and 25,000 or less. Below, it is more preferably 19,000 or more and 24,000 or less, still more preferably 20,500 or more and 23,000 or less.
• the polycarbonate-polyorganosiloxane copolymer (A) of the present invention can be produced, for example, by using a diol monomer (a1) and a polyorganosiloxane (a2) as raw material monomers.
• the diol monomer (a1) is not particularly limited as long as it has a structure represented by the following general formula (a1).
• an aromatic dihydroxy compound or an aliphatic dihydroxy compound can be used as the diol monomer (a1).
• R 10 in the above general formula (a1) is as described above, and preferred ones are also the same.
• the polyorganosiloxane (a2) preferably has a structure represented by any one of the following general formulas (a2-1) to (a2-3).
• R 1 to R 8 , z 1 , z 2 , u 1 , u 2 , n a n b , and ⁇ represent the same meanings as above.
• the method for producing polyorganosiloxane (a2) is not particularly limited.
• ⁇ , ⁇ -dihydrogenorganopentasiloxane is synthesized by reacting cyclotrisiloxane and disiloxane in the presence of an acidic catalyst, and then, Addition reaction of an oligomer or polymer (for example, polyalkylene ether, polyester, polycarbonate, etc.) modified with an allyl group at one end to the ⁇ , ⁇ -dihydrogenorganopentasiloxane in the presence of a hydrosilylation reaction catalyst.
• an oligomer or polymer for example, polyalkylene ether, polyester, polycarbonate, etc.
• octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the resulting ⁇ , ⁇ -dihydrogen organ
• a polyorganosiloxane can be obtained by subjecting a polysiloxane to an addition reaction with an oligomer or polymer modified with an allyl group at one end in the presence of a hydrosilylation catalyst in the same manner as described above.
• ⁇ , ⁇ -dihydrogenorganopolysiloxane can be used by appropriately adjusting its average repeating number na depending on the polymerization conditions, or it can be used by using a commercially available ⁇ , ⁇ -dihydrogenorganopolysiloxane.
• an oligomer modified with an allyl group at one end can be used with its average repeating number n b appropriately adjusted depending on the polymerization conditions, or a commercially available oligomer modified with an allyl group at one end can be used.
• polyethylene glycol modified with an allyl group at one end can be produced with reference to Japanese Patent No. 5,652,691 and the like.
• allyl group-modified polyethylene glycols include UNIOX PKA-5001, UNIONOX PKA-5002, UNIONOX PKA-5003, UNIONOX PKA-5004, UNIONOX PKA-5005 and the like manufactured by NOF Corporation.
• the polycarbonate-polyorganosiloxane copolymer (A) can be produced by polymerizing raw material monomers by an interfacial polymerization method or a melt polymerization method (ester exchange method).
• the polycarbonate-polyorganosiloxane copolymer (A) is preferably obtained by a melt polymerization method.
• an interfacial polymerization method for example, the method described in JP 2014-80462 A and the like can be adopted.
• a polycarbonate-polyorganosiloxane copolymer is obtained by reacting polyorganosiloxane (a2), which is a raw material monomer, a diol monomer (a1), and a carbonate ester compound, preferably in the presence of a basic catalyst, by a melt polymerization method.
• Combined (A) can be produced.
• a terminal terminator may be further added to carry out the polymerization reaction.
• the present invention provides a method for producing a polycarbonate-polyorganosiloxane copolymer (A), which includes a step of reacting a polyorganosiloxane (a2), a diol monomer (a1), and a carbonate ester compound by a melt polymerization method.
• a melt polymerization method includes a step of reacting a polyorganosiloxane (a2), a diol monomer (a1), and a carbonate ester compound by a melt polymerization method.
• the step of reacting by the melt polymerization method is preferably carried out in the presence of a basic catalyst.
• the melt polymerization method does not require a solvent such as methylene chloride, which has a high environmental impact and tends to be expensive, and is therefore preferable from the viewpoint of environmental impact and economic efficiency.
• melt polymerization method does not require a solvent such as methylene chloride, which is required in the interfacial polymerization method, and is therefore environmentally and economically advantageous.
• highly toxic phosgene which is used as a carbonate source in the interfacial polymerization method, is not used, it is advantageous in terms of production.
• carbonate ester compound examples include diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds.
• Examples of the diaryl carbonate compound include a compound represented by the following general formula (11) and a compound represented by the following general formula (12).
• Ar 1 and Ar 2 each represent an aryl group, and may be the same or different from each other.
• Ar 3 and Ar 4 each represent an aryl group, which may be the same or different from each other, and D 1 is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound. show. ]
• dialkyl carbonate compounds examples include compounds represented by the following general formula (13) and compounds represented by the following general formula (14).
• R 21 and R 22 each represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and may be the same or different from each other.
• R 23 and R 24 each represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same or different, and D 2 is Indicates a residue obtained by removing two hydroxyl groups from an aromatic dihydroxy compound or an aliphatic dihydroxy compound.
• alkylaryl carbonate compound examples include a compound represented by the following general formula (15) and a compound represented by the following general formula (16).
• Ar 5 represents an aryl group
• R 25 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms
• Ar 6 is an aryl group
• R 26 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms
• D 1 is a hydroxyl group 2 from the aromatic dihydroxy compound or aliphatic dihydroxy compound. Residues excluding those are shown.
• diaryl carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, and bisphenol A bisphenyl carbonate.
• dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate.
• alkylaryl carbonate compound include methylphenyl carbonate, ethylphenyl carbonate, butylphenyl carbonate, cyclohexylphenyl carbonate, and bisphenol A methylphenyl carbonate.
• a preferred carbonate compound is diphenyl carbonate.
• One or more carbonate ester compounds can be used in the production of the polycarbonate-polyorganosiloxane copolymer (A).
• Terminal terminator When producing the polycarbonate-polyorganosiloxane copolymer (A), a terminal capping agent can be used as necessary.
• the terminal capping agent any known terminal capping agent used in the production of polycarbonate resins may be used.
• specific compounds thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, and p-tert-octylphenol.
• Examples include cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.
• Branching agent can also be used when producing the polycarbonate-polyorganosiloxane copolymer (A).
• Branching agents include phloroglucin, trimellitic acid, 1,1,1-tris(4-hydroxyphenyl)ethane, 1-[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl)ethyl]-4-[ ⁇ ' , ⁇ '-bis(4"-hydroxyphenyl)ethyl]benzene, ⁇ , ⁇ ', ⁇ "-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, and isatin bis(o-cresol), etc. can be mentioned.
• the polycarbonate-polyorganosiloxane copolymer (A) can be produced by a melt polymerization method, for example, according to the following procedure.
• a transesterification reaction is performed between the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound.
• the amount of the carbonate ester compound relative to the diol monomer is preferably 0.9 to 1.2 times by mole, more preferably 0.98 to 1.02 times by mole.
• the amount of the terminal capping agent when the amount of the terminal capping agent is in the range of 0.05 to 10 mol% based on the total amount of the diol monomer (a1) and the polyorganosiloxane (a2), the resulting polycarbonate - Since the hydroxyl group terminals of the polyorganosiloxane copolymer are sufficiently sealed, it is preferable from the viewpoint that a polycarbonate resin having excellent heat resistance and water resistance can be obtained.
• the amount of the terminal capping agent based on the total amount of the diol monomer (a1) and the polyorganosiloxane (a2) is more preferably 1 to 6 mol%.
• the terminal capping agent may be added in its entirety to the reaction system in advance, or a portion thereof may be added in advance to the reaction system, and the remainder may be added as the reaction progresses. It is preferred that an antioxidant be added to the reactor simultaneously with the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound, and the transesterification reaction be carried out in the presence of the antioxidant. As a result, for example, deterioration due to heat, oxidation, etc.
• the reaction temperature for carrying out the transesterification reaction is not particularly limited, and may be, for example, in the range of 100 to 330°C, preferably in the range of 180 to 300°C, and more preferably in the range of 200 to 240°C. Further, it is preferable to gradually raise the temperature from 180°C to 300°C as the reaction progresses. If the transesterification temperature is 100°C or higher, the reaction rate will be sufficiently fast, whereas if it is 330°C or lower, many side reactions will not occur and the resulting polycarbonate-polyorganosiloxane copolymer will be colored. Problems such as poor appearance, such as scratches, are less likely to occur.
• the reaction pressure is set depending on the vapor pressure of the monomer used and the reaction temperature. There are no particular limitations as long as the settings are such that the reaction is carried out efficiently. For example, in the early stage of the reaction, the atmospheric pressure (normal pressure) or pressurized state is from 1 to 50 atm (760 to 38,000 torr), and in the later stage of the reaction, the pressure is reduced, and finally the pressure is 1.33 to 1.
• the pressure is preferably 33 ⁇ 10 4 Pa (0.01 to 100 torr).
• the reaction time may be carried out until the target molecular weight is reached, and is, for example, 0.2 to 10 hours.
• the above transesterification reaction is carried out, for example, in the absence of an inert solvent, but if necessary, it is carried out in the presence of 1 to 150 parts by mass of an inert solvent based on 100 parts by mass of the resulting polycarbonate resin. It's okay.
• Inert solvents include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; and; tricyclo[5.2.1.0 2,6 ]decane, cyclooctane, and cycloalkanes such as cyclodecane. It may be carried out under an inert gas atmosphere if necessary.
• inert gases examples include gases such as argon, carbon dioxide, dinitrogen monoxide, and nitrogen, chlorofluorohydrocarbons, alkanes such as ethane and propane, and ethylene. and alkenes such as propylene.
• the basic catalyst is at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing aryl groups, and metal compounds. can be mentioned. These compounds can be used alone or in combination.
• Basic catalysts include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxide; quaternary phosphonium salts containing aryl groups, etc. is preferably used.
• One type of basic catalyst can be used alone or two or more types can be used in combination.
• Alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus
• Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, discesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.
• alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and diacetic acid. Examples include barium.
• nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further examples include tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole.
• bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.
• metal compound examples include zinc aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.
• quaternary phosphonium salts containing an aryl group include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetra Tetra(aryl or alkyl)phosphonium hydroxides such as methylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetra Phenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphen
• the quaternary phosphonium salt containing an aryl group is preferably combined with a nitrogen-containing organic basic compound, such as a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate.
• the amount of the basic catalyst used is preferably 1 x 10 -9 to 1 x 10 -2 mol, preferably 1 x 10 -8 to 1 x 10 -2 mol, more preferably 1 x 10 -2 mol, per 1 mol of diol monomer (a1). can be selected within the range of 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 3 mol.
• a catalyst deactivator can also be added in the latter stage of the reaction.
• known catalyst deactivators are effectively used.
• the catalyst deactivator include ammonium salts of sulfonic acids and phosphonium salts of sulfonic acids.
• the amount of catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst, and more It can be used preferably in a proportion of 0.5 to 10 moles, more preferably in a proportion of 0.8 to 5 moles. It is preferable to mix the antioxidant after adding the catalyst deactivator and completing the polymerization reaction. By mixing an antioxidant after the polymerization reaction is completed and then taking out the obtained polycarbonate-polyorganosiloxane copolymer from the reactor, it is possible to prevent heat, oxygen, etc. during the subsequent compounding process and the process of obtaining a molded product.
• Deterioration of the polycarbonate-polyorganosiloxane copolymer can be reduced. By doing so, it is possible to obtain resin pellets and molded bodies with even better appearance such as color tone and surface appearance, and effects such as being able to reduce the formation of undesirable gel components can also be obtained.
• the reaction in the melt polymerization method may be carried out either continuously or batchwise.
• the reactor used for melt polymerization is a vertical reactor equipped with anchor-type stirring blades, max blend stirring blades, or helical ribbon-type stirring blades, or a horizontal reaction apparatus equipped with paddle blades, lattice blades, spectacle blades, etc. Any device may be used. Furthermore, an extruder type equipped with a screw may be used. In the case of a continuous type, it is preferable to use such reaction devices in appropriate combinations.
• the polycarbonate resin composition of the present invention contains the above-mentioned polycarbonate-polyorganosiloxane copolymer (polycarbonate-polyorganosiloxane copolymer (A)).
• Well-known additives can be used in the polycarbonate resin composition of the present invention as long as they do not impair the properties of the polycarbonate-polyorganosiloxane copolymer (A).
• additives can be added to the polycarbonate resin composition of the present invention depending on the purpose and necessity.
• additives include various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, and ultraviolet absorbers. agent, mold release agent, etc.
• the antioxidant can suppress the decomposition of the resin during production or molding of the thermoplastic resin composition.
• the method for producing the polycarbonate resin composition of the present invention is not particularly limited as long as it includes a step of mixing the polycarbonate-polyorganosiloxane copolymer and any additives.
• it can be produced by mixing a polycarbonate-polyorganosiloxane copolymer and arbitrary additives using a mixer or the like, and melt-kneading the mixture.
• Melt kneading is carried out by a commonly used method, such as a method using a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, twin screw extruder, co-kneader, multi-screw extruder, etc. be able to.
• the heating temperature during melt-kneading is normally selected appropriately within the range of about 150 to 300°C, preferably about 220 to 300°C.
• the molded article of the present invention contains the polycarbonate resin composition of the present invention.
• the molded article is produced using a melt-kneaded product of a polycarbonate resin composition or pellets obtained through melt-kneading as a raw material, using an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, It can be manufactured by vacuum forming method, foam molding method, etc.
• the thickness of the molded body can be arbitrarily set depending on the application, and in particular when transparency of the molded body is required, the thickness is preferably 0.2 to 4.0 mm, and 0.3 to 3.0 mm. More preferably, 0.3 to 2.0 mm is even more preferable. When the thickness of the molded body is 0.2 mm or more, no warping occurs and good mechanical strength can be obtained. Moreover, if the thickness of the molded body is 4.0 mm or less, high transparency can be obtained.
• a hard coat film, an antifogging film, an antistatic film, or an antireflection film may be formed on the molded body as necessary, or a composite film of two or more types may be formed. Among these, it is particularly preferable that a hard coat film is formed because it has good weather resistance and can prevent the surface of the molded product from being worn out over time.
• the material of the hard coat film is not particularly limited, and known materials such as acrylate hard coat agents, silicone hard coat agents, and inorganic hard coat agents can be used.
• the molded article containing the polycarbonate resin according to the present invention can be used in parts that require transparency and rigidity, as well as scratch resistance and weather resistance, such as 1) automobile use such as sunroofs, door visors, rear windows, and side windows; Parts, 2) Architectural parts such as architectural glass, soundproof walls, carports, sunrooms and gratings, 3) Windows for railway vehicles and ships, 4) Televisions, radio cassettes, video cameras, video tape recorders, audio Various parts for players, DVD players, telephones, displays, computers, registers, copiers, printers, facsimiles, etc., parts for electrical equipment such as outer panels and housing parts, 5) Mobile phones, PDAs, cameras, slide projectors.
• Parts for precision equipment such as cases and covers for precision equipment such as watches, calculators, measuring instruments, display devices, etc.
• Agricultural parts for greenhouses, greenhouses, etc. Lighting covers, blinds, interior equipment, etc. It can be suitably used for furniture parts, etc.
• Synthesis Example 2 Production of PDMS-2 100 g of ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 61 and oxyethylene instead of ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 45
• Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1, except that 31.4 g of polyethylene glycol modified with an allyl group at one end and having an average repeating number of oxyethylene units of 15 was used instead of polyethylene glycol modified with an allyl group at one end having an average repeating number of oxyethylene units of 12. , a modified polyorganosiloxane PDMS-2 was obtained.
• Synthesis Example 3 Production of PDMS-3 ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 24 and oxyethylene unit instead of ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 45
• a modified polyorganosiloxane PDMS-3 was obtained in the same manner as in Synthesis Example 1, except that 63.8 g of polyethylene glycol modified with an allyl group at one end and having an average repetition number of 12 was used.
• Synthesis Example 4 Production of PDMS-4 Instead of ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 45, polyorganosiloxane with an average chain length of 30 and an average repeating number of oxyethylene units of 12 were used.
• Modified polyorganosiloxane PDMS-4 was obtained in the same manner as in Synthesis Example 1 except that 8.9 g of ethylene glycol monoallyl ether was used in place of the allyl group-modified polyethylene glycol at one end. Note that ethylene glycol monoallyl ether has one oxyethylene unit.
• Synthesis Example 5 Production of PDMS-5 Instead of polyethylene glycol modified with an allyl group on one end and with an average repeating number of oxyethylene units of 12, polyethylene glycol modified with an allyl group on one end with an average repeating number of oxyethylene units of 8 (NOF Modified polyorganosiloxane PDMS-5 was obtained in the same manner as Synthesis Example 1 except that 24.2 g of Uniox PK-5002 (manufactured by Co., Ltd.) was used.
• Synthesis Example 6 Production of PDMS-6 Instead of polyethylene glycol modified with an allyl group on one end and with an average repeating number of oxyethylene units of 12, polyethylene glycol modified with an allyl group on one end with an average repeating number of oxyethylene units of 38 (NOF Modified polyorganosiloxane PDMS-6 was obtained in the same manner as in Synthesis Example 1 except that 102.0 g of Uniox PK-5005 (manufactured by Co., Ltd.) was used.
• Synthesis Example 7 Production of PDMS-7 100 g of polyorganosiloxane with an average chain length of 88 instead of ⁇ , ⁇ -dihydrogenorganopolysiloxane with an average chain length of 45 and an average repeating number of oxyethylene units of 12 Modified polyorganosiloxane PDMS- I got a 7.
• Example 1 A polycarbonate-polyorganosiloxane copolymer was produced using the following raw materials and conditions.
• Bisphenol A Bisphenol A (BisP-A; 2,489.9 g) as a diol monomer and carbonate ester were placed in a 10 L stainless steel reactor equipped with a stirring device, a nitrogen inlet tube, a heater, a trap for capturing distilled phenol, and a pressure reducing device.
• Diphenyl carbonate (DPC; 2,500 g) as a compound (molar ratio of each raw material: BisP-A/DPC 100/107) and 87.1 g of modified polyorganosiloxane PDMS-1 obtained in Synthesis Example 1 were added, These raw material monomers were completely melted at °C, and then the inside of the reactor was purged with nitrogen. 1.64 mL of 0.01 mol/L sodium hydroxide (1.5 x 10 -6 times the number of moles of all diol monomers) was added as a catalyst to start polymerization, and the temperature inside the reactor rose over about 60 minutes.
• the temperature was raised to 180° C., the pressure inside the reactor was reduced to 200 mmHg (26.6 kPa), and the reaction conditions were maintained until the amount of phenol distilled was 0.2 L.
• the temperature inside the reactor was raised to 240° C. over about 120 minutes, and the reaction conditions were maintained until 1.5 L of phenol was distilled out.
• the temperature inside the reactor was raised to 280°C over about 120 minutes, and the pressure inside the reactor was reduced to 1 mmHg (0.1 kPa) or less, and 2 L or more of phenol was distilled out until the specified stirring torque was reached.
• the reaction continued. Thereafter, nitrogen was introduced to raise the pressure to normal pressure, and 0.037 g of butyl p-toluenesulfonate (10 times the number of moles of sodium hydroxide added) was added as a catalyst deactivator.
• antioxidant 1 and antioxidant 2 were added to the reactor in an amount of 0.05 parts by mass each based on the theoretical yield of the polycarbonate-polyorganosiloxane copolymer, and thoroughly stirred. Thereafter, high pressure nitrogen was introduced into the reactor to extrude the molten polycarbonate-polyorganosiloxane copolymer strand from the bottom of the reactor. The obtained strands were cut with a pelletizer to obtain pellets of polycarbonate-polyorganosiloxane copolymer PC-POS1.
• the raw materials used for production are as follows. ⁇ Bisphenol A (BisP-A) [manufactured by Idemitsu Kosan Co., Ltd.] ⁇ Diphenyl carbonate (DPC) [manufactured by Mitsui Chemicals Fine Co., Ltd.] ⁇ 0.01 mol/L sodium hydroxide aqueous solution [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] ⁇ Antioxidant (C): Antioxidant 1: Tris(2,4-di-tert-butylphenyl) phosphite [manufactured by BASF Japan Co., Ltd., Irgafos168] Antioxidant 2: Pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Japan Co., Ltd., Irganox1010]
• Example 2 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of modified polyorganosiloxane PDMS-1 was used.
• Example 3 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 244.8 g of modified polyorganosiloxane PDMS-1 was used.
• Example 4 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 117.3 g of PDMS-2 obtained in Synthesis Example 2 was used as the modified polyorganosiloxane.
• Example 5 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-2 was used as the modified polyorganosiloxane.
• Example 6 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 244.8 g of PDMS-2 was used as the modified polyorganosiloxane.
• Example 7 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-1 was used as the modified polyorganosiloxane and the reaction was continued for 30 minutes even after the predetermined torque was reached.
• Example 8 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 117.3 g of PDMS-2 was used as the modified polyorganosiloxane and the reaction was continued for 30 minutes even after the predetermined torque was reached.
• Comparative example 1 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-3 was used as the modified polyorganosiloxane.
• Comparative example 2 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-4 was used as the modified polyorganosiloxane.
• Comparative example 3 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-5 was used as the modified polyorganosiloxane.
• Comparative example 4 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 312.8 g of PDMS-5 was used as the modified polyorganosiloxane.
• Comparative example 5 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-6 was used as the modified polyorganosiloxane.
• Comparative example 6 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-7 was used as the modified polyorganosiloxane.
• Comparative example 7 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-8 was used as the polyether-modified polyorganosiloxane.
• Comparative example 8 Pellets of polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 8.4 g of PDMS-1 was used as the modified polyorganosiloxane.
• Probe TH5 Compatible with 5 ⁇ NMR sample tube Observation range: -5 to 15 ppm Observation center: 5ppm Pulse repetition time: 9 seconds Pulse width: 45° Integration number: 256 times NMR sample tube: 5 ⁇ Sample amount: 30-40mg
• Solvent Deuterated chloroform Measurement temperature: Room temperature A: Peak integral value of the meta position of the phenyl moiety observed around ⁇ 7.3 to 7.5 B: Methylene group of the PEG moiety observed around ⁇ 3.3 to 4.5 Peak integral value C: Peak integral value of methyl group of bisphenol A moiety observed around ⁇ 1.50 to 2.00 D: Methyl group of dimethylsiloxane moiety observed around ⁇ -0.02 to 0.4 Peak integral value E: Peak integral value of the methylene group at the end of dimethylsiloxane observed around ⁇ 0.52

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