WO2019131973A1 - ポリカーボネート-ポリオルガノシロキサン共重合体 - Google Patents
ポリカーボネート-ポリオルガノシロキサン共重合体 Download PDFInfo
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- WO2019131973A1 WO2019131973A1 PCT/JP2018/048373 JP2018048373W WO2019131973A1 WO 2019131973 A1 WO2019131973 A1 WO 2019131973A1 JP 2018048373 W JP2018048373 W JP 2018048373W WO 2019131973 A1 WO2019131973 A1 WO 2019131973A1
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- carbon atoms
- polycarbonate
- polyorganosiloxane
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Definitions
- the present invention relates to polycarbonate-polyorganosiloxane copolymers. More particularly, the present invention relates to a polycarbonate-polyorganosiloxane copolymer having flexibility and excellent transparency.
- Polycarbonate resins are superior in mechanical strength and moldability to acrylic resins, but tend to be inferior in flexibility.
- An object of the present invention is to provide a polycarbonate-polyorganosiloxane copolymer having both excellent flexibility and transparency.
- the present inventors have found that a polycarbonate-polyorganosiloxane copolymer having specific structural units and having specific conditions (hereinafter sometimes abbreviated as a PC-POS copolymer) is flexible. It has been found that it is possible to maintain the excellent transparency and mechanical strength possessed by the polycarbonate-polyorganosiloxane copolymer as well as the properties. That is, the present invention relates to the following [1] to [10].
- a polycarbonate block (A-1) consisting of repeating units represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing repeating units represented by the following general formula (II)
- a polycarbonate-polyorganosiloxane copolymer (A) which satisfies the following requirements (1) to (3).
- the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is more than 40% by mass and 70% by mass or less.
- the viscosity average molecular weight is 10,000 or more and 23,000 or less.
- the polycarbonate block (A-1) includes a polycarbonate block in which a and b in the following general formula (I) are 0, and X represents an isopropylidene group.
- R 1 and R 2 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 represents 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 12 carbon atoms, or a cyclopentadiene having 5 to 15 carbon atoms
- R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- a and b each independently represent an integer of 0 to 4;
- R 33 and R 34 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 31 represents 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, an arylene group having 6 to 12 carbon atoms, It shows a fluorenediyl group, an aryl alkylene group having 7 to 15 carbon atoms, and an aryl alkylidene group having 7 to 15 carbon atoms.
- R 35 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- t represents the average chain length of the polyorganosiloxane.
- polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [5], which has a weight average molecular weight of 40,000 or less.
- polyorganosiloxane block (A-2) contains a unit represented by at least one of the following general formulas (II-I) to (II-III) Polycarbonate-polyorganosiloxane copolymer as described in 1 or 2.
- R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
- the plurality of R 3 to R 6 may be identical to or different from one another.
- Y is -R 7 O -, - R 7 COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or -R 7 O—R 10 —O— is shown, and a plurality of Y may be the same as or different from each other.
- R 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group.
- R 8 represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 9 represents a diarylene group.
- R 10 represents a linear, branched or cyclic alkylene group or a diarylene group.
- ⁇ 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.
- n represents the chain length of the polyorganosiloxane
- n-1 and p and q each represent an integer of 1 or more representing the repeating number of the polyorganosiloxane unit
- the sum of p and q is n-2.
- V The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [7], wherein the polyorganosiloxane block (A-2) is represented by the following general formula (V). [Wherein, R 3 to R 6 and n-1 are the same as those described in the general formulas (II-I) to (II-III).
- R 15 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- a polycarbonate-polyorganosiloxane copolymer having both excellent flexibility and transparency can be obtained.
- the polycarbonate-polyorganosiloxane copolymer of the present invention will be described in detail.
- the preferable definition can be arbitrarily adopted, and a combination of preferable ones can be said to be more preferable.
- the description of “XX to YY” means “XX or more and YY or less”.
- the polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block (A-1) comprising repeating units represented by the following general formula (I) and a poly containing a repeating unit represented by the following general formula (II)
- the polycarbonate-polyorganosiloxane copolymer (A) containing an organosiloxane block (A-2) is characterized by satisfying the following requirements (1) to (3).
- the content of the polyorganosiloxane block (A-2) is more than 40% by mass and 70% by mass or less.
- the viscosity average molecular weight is 10,000 or more and 23,000 or less.
- the polycarbonate block (A-1) includes a polycarbonate block in which a and b in the general formula (I) are 0 and X represents an isopropylidene group.
- R 1 and R 2 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 represents 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 12 carbon atoms, or a cyclopentadiene having 5 to 15 carbon atoms
- R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- a and b each independently represent an integer of 0 to 4; ]
- the polycarbonate block (A-1) represented by the general formula (I) will be described in detail.
- a halogen atom which R ⁇ 1 > and R ⁇ 2 > respectively independently show in said general formula (I) a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
- the alkyl group represented by R 1 and R 2 are each independently a methyl group, an ethyl group, n- propyl group, and isopropyl group, various butyl groups ( "Various", a straight chain and any branched And the same applies hereinafter), various pentyl groups, and various hexyl groups.
- an alkoxy group which R ⁇ 1 > and R ⁇ 2 > respectively independently show the case where an alkyl group site
- Examples of the alkylene group represented by X include a methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like, and an alkylene group having 1 to 5 carbon atoms is preferable.
- Examples of the alkylidene group represented by X include an ethylidene group, an isopropylidene group and the like.
- Examples of the cycloalkylene group represented by X include a cyclopentadiyl group, a cyclohexanediyl group, a cyclooctanediyl group and the like, and a cycloalkylene group having a carbon number of 5 to 10 is preferable.
- arylene group which X represents a phenylene group, a naphthylene group, a biphenylene group etc.
- a cycloalkylidene group which X represents a cyclohexylidene group, 3, 5, 5- trimethylcyclohexylidene group, 2-adamantylidene group etc. are mentioned, for example, A C5-C10 cycloalkylidene group is preferable. And a cycloalkylidene group having 5 to 8 carbon atoms is more preferable.
- Examples of the aryl moiety of the aryl alkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl group, naphthyl group, biphenyl group and anthryl group.
- Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl group, naphthyl group, biphenyl group and anthryl group.
- a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1. Among them, those in which a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or those in which a and b are 0 and X is an alkylidene group, particularly isopropylidene group are preferable. It is.
- a polycarbonate block in which a and b in the general formula (I) are 0 and X represents an isopropylidene group (hereinafter abbreviated as BPA block) May be included as a requirement.
- the amount of BPA block in the polycarbonate block (A-1) is preferably 90% by mass or more, more preferably 90.9% by mass or more, still more preferably 93.3% by mass or more, particularly preferably 95% by mass or more Preferably it is 100 mass%. It is preferable from the viewpoint of transparency when the BPA block amount is in the above range.
- polycarbonate block (A-1) plural types of polycarbonate blocks may be contained as long as the requirements of the above (3) are satisfied.
- the polycarbonate block (A-1) contains a plurality of types of blocks, the total of the BPA block and the other polycarbonate blocks is 100% by mass.
- the halogen atom shown by R 3 or R 4 are each independently a fluorine atom, a chlorine atom, a bromine atom, and iodine atom.
- the alkyl group independently represented by R 3 or 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.
- the alkoxy group shown R 3 or R 4 each independently include the alkyl group moiety is a said alkyl group.
- the aryl group represented by R 3 or R 4 are each independently a phenyl group, a naphthyl group, and the like.
- Each of R 3 and R 4 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, both of which are methyl groups. It is more preferable that
- the polyorganosiloxane block containing the repeating unit represented by the general formula (II) preferably has units represented by the following general formulas (II-I) to (II-III).
- R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
- the plurality of R 3 to R 6 may be identical to or different from one another.
- Y is -R 7 O -, - R 7 COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O- or -R 7 O -R 10 -O- is shown, and a plurality of Y may be the same as or different from each other.
- R 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl substituted alkylene group, a substituted or unsubstituted arylene group or a diarylene group.
- R 8 represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 9 represents a diarylene group.
- R 10 represents a linear, branched or cyclic alkylene group or a diarylene group.
- ⁇ 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.
- n represents the chain length of the polyorganosiloxane
- n-1 and p and q each represent an integer of 1 or more representing the repeating number of the polyorganosiloxane unit
- the sum of p and q is n-2.
- the halogen atom represented by R 3 to R 6 independently includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- Examples of the alkyl group independently represented by R 3 to R 6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.
- Examples of the alkoxy group represented by R 3 to R 6 independently include the case where the alkyl group moiety is the above-mentioned alkyl group.
- the aryl group represented by R 3 to R 6 independently includes a phenyl group, a naphthyl group and the like.
- Each of R 3 to R 6 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. It is preferred that all of R 3 to R 6 in the general formulas (II-I), (II-II) and / or (II-III) are methyl groups.
- Y is -R 7 shows O -, - R 7 COO - , - R 7 NH -, - R 7 NR 8 -, - at R 7 COO-R 9 -O- or -R 7 O-R 10 -O-
- the linear or branched alkylene group represented by R 7 includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and the cyclic alkylene group includes 5 to 15 carbon atoms, preferably carbon atoms There may be 5 to 10 cycloalkylene groups.
- an aromatic ring may have a substituent such as an alkoxy group or an alkyl group, and as a specific structure thereof, for example, the following general formula (i) or ( The structure of ii) can be shown.
- the alkylene group is bonded to Si.
- c represents a positive integer and is usually an integer of 1 to 6)
- the diarylene group represented by R 7 , R 9 and R 10 is a group in which two arylene groups are directly or via a divalent organic group, and more specifically, -Ar 1 -W- It is a group having a structure represented by Ar 2- .
- Ar 1 and Ar 2 each represent an arylene group, and W represents a single bond or a divalent organic group.
- the divalent organic group represented by W is, for example, isopropylidene, methylene, dimethylene or trimethylene.
- Examples of the arylene group represented by R 7 , Ar 1 and Ar 2 include arylene groups having 6 to 14 ring carbon atoms, such as phenylene group, naphthylene group, biphenylene group, anthrylene group and the like.
- arylene groups may have any substituent such as an alkoxy group or an alkyl group.
- the alkyl group represented by R 8 is a linear or branched one having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
- the alkenyl group includes linear or branched ones having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms.
- Examples of the aryl group include phenyl group and naphthyl group.
- Examples of the aralkyl group include phenylmethyl and phenylethyl.
- the linear, branched or cyclic alkylene group represented by R 10 is the same as R 7 .
- Y is preferably -R 7 O-, and R 7 is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, and an organic residue derived from allylphenol or eugenol Organic residues derived from are more preferred.
- R 7 is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, and an organic residue derived from allylphenol or eugenol Organic residues derived from are more preferred.
- the PC-POS copolymer of the present invention comprises a polyorganosiloxane block (A-2) represented by the following general formula (V).
- A-2 polyorganosiloxane block
- R 3 to R 6 and n are the same as those described in the general formulas (II-I) to (II-III).
- R 15 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- the number of repetition of the polyorganosiloxane block (A-2) in the PC-POS copolymer is preferably 10 or more and less than 90, and more preferably 10 or more and 40 or less. Specifically, it is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, preferably less than 90, more preferably 80 or less, still more preferably 60 or less, still more preferably 45 or less More preferably, it is 40 or less, particularly preferably less than 40.
- the repeat number is calculated by nuclear magnetic resonance (NMR) measurement.
- the content of the polyorganosiloxane block (A-2) in (1) PC-POS copolymer (A) exceeds 40% by mass and 70% by mass It is a requirement that By setting the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer to more than 40% by mass, a copolymer excellent in flexibility can be obtained.
- the content of the polyorganosiloxane block (A-2) is 70% by mass or less, there is no noticeable tack and a copolymer capable of maintaining the shape as a flexible molded product is obtained.
- the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) of the present invention is preferably 41% by mass or more, more preferably 45% by mass or more, and preferably 65% by mass The following content is more preferably 60% by mass or less.
- the PC-POS copolymer of the present invention further has (2) a viscosity average molecular weight (Mv) of 10,000 or more and 23,000 or less.
- the viscosity average molecular weight (Mv) can be adjusted by using a molecular weight modifier (end stopper) or the like, or by reaction conditions. By making viscosity average molecular weight into the range of (2), it can be set as the copolymer which is excellent in moldability.
- the viscosity average molecular weight (Mv) is preferably 12,000 or more, more preferably 14,000 or more, still more preferably 16,000 or more, preferably 21,500 or less, more preferably 20,500 or less, more preferably Is 19,500 or less, more preferably 18,500 or less, particularly preferably 18,000 or less.
- the viscosity average molecular weight (Mv) is a value calculated from the following Schnell's equation by measuring the intrinsic viscosity [ ⁇ ] of the methylene chloride solution at 20 ° C.
- the weight average molecular weight (Mw) of the PC-POS copolymer of the present invention is preferably 40,000 or less. When the weight average molecular weight (Mw) is in the above range, a PC-POS copolymer excellent in flexibility can be obtained.
- the weight average molecular weight (Mw) of the PC-POS copolymer is more preferably 37,000 or less, still more preferably 35,000 or less, still more preferably 30,000 or less.
- the weight average molecular weight (Mw) is preferably 20,000 or more, more preferably 23,000 or more.
- the PC-POS copolymer (A) of the present invention preferably has a molecular weight distribution (Mw / Mn) of 2.1 or more and 3.9 or less.
- Mw / Mn molecular weight distribution
- the molecular weight distribution Mw / Mn of the PC-POS copolymer is in the above-mentioned range, nonuniformity due to random movement and phase separation is suppressed when molding the PC-POS copolymer, and transparency is high, and It is preferable because a molded article with easy control of flexibility can be obtained.
- the above-mentioned molecular weight distribution Mw / Mn of the PC-POS copolymer (A) is more preferably 2.3 or more, still more preferably 2.4 or more, still more preferably 2.5 or more, and still more preferably 2.7. Or more, particularly preferably 2.8 or more, more preferably 3.5 or less, still more preferably 3.0 or less, and particularly preferably 2.9 or less.
- the PC-POS copolymer (A) can be produced by a known production method such as interfacial polymerization method (phosgene method), pyridine method, transesterification method and the like.
- interfacial polymerization method phosgene method
- pyridine method pyridine method
- transesterification method a known production method
- an interfacial polymerization method is employed in which polyorganosiloxane is added to a reaction system for polymerizing dihydric phenol and a carbonate precursor and copolymerized, an organic phase containing PC-POS copolymer, unreacted matter, catalyst residue, etc.
- the separation process from the aqueous phase containing water is easy, and the separation between the organic phase containing the PC-POS copolymer and the aqueous phase is facilitated in each washing process by alkaline washing, acid washing, and pure water (ion-exchange water) washing It is preferable because a PC-POS copolymer can be obtained efficiently.
- a method for producing a PC-POS copolymer for example, the method described in JP-A-2014-80462 can be referred to.
- an aqueous solution of an alkaline compound of a dihydric phenol compound (bisphenol A or the like) (a bisphenol A or the like) is dissolved in a non-water-soluble organic solvent (methylene chloride or the like) and a polycarbonate oligomer prepared in advance and polyorganosiloxane described later.
- a non-water-soluble organic solvent methylene chloride or the like
- a polycarbonate oligomer prepared in advance and polyorganosiloxane described later.
- PC-POS copolymers can also be prepared by copolymerizing polyorganosiloxanes, dihydric phenols, phosgene, carbonates or chloroformates.
- the PC-POS copolymer (A) contained in the polycarbonate resin composition of the present invention is reacted, for example, with a dihydric phenol after the polycarbonate oligomer and the polyorganosiloxane raw material are reacted in an organic solvent.
- the solid content weight (g / L) of the polycarbonate oligomer in 1 L of the mixed solution of the above organic solvent and the polycarbonate oligomer is 200 g / L or less It is preferable to be in the range of More preferably, it is 180 g / L or less, more preferably 170 g / L or less.
- it is preferably 20 g / L or more, more preferably 30 g / L or more, and still more preferably 40 g / L or more.
- R 3 to R 6 , Y, ⁇ , n-1, p and q are as described above, and so are the specific examples and preferable ones.
- Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same as or different from each other.
- R 3 to R 6 , n and R 8 are as defined above, and preferred ones are also the same.
- c represents a positive integer and is usually an integer of 1 to 6.
- the phenol-modified polyorganosiloxane represented by the above general formula (1-1) is preferable in view of the easiness of polymerization.
- ⁇ , ⁇ -bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane which is a kind of the compound represented by the above general formula (1-2)
- ⁇ , ⁇ -bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane which is one of the compounds, is preferable.
- R 3 and R 4 are as defined above.
- the average chain length of the polyorganosiloxane block represented by the general formula (4) is (r ⁇ m), and the range of (r ⁇ m) is the same as the above n.
- the polyorganosiloxane block (A-2) preferably has a unit represented by the following general formula (II-IV).
- the polyorganosiloxane block (A-2) may have a structure represented by the following general formula (II-V).
- R 18 to R 21 each independently represent a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
- R 22 is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms.
- Q 2 is a divalent aliphatic group having 1 to 10 carbon atoms.
- n-1 represents the number of repetition of the polyorganosiloxane block, and the range is as described above.
- examples of the alkyl group having 1 to 13 carbon atoms which R 18 to R 21 independently represent are methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, and various kinds
- a pentyl group, various hexyl groups, various heptyl groups, various octyl groups, 2-ethylhexyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, and various tridecyl groups can be mentioned.
- R 18 to R 21 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and all of them are more preferably a methyl group.
- Examples of the alkyl group having 1 to 6 carbon atoms represented by R 22 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 halogen atom R 22 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
- Examples of the alkoxy group having 1 to 6 carbon atoms represented by R 22 include the case where the alkyl group moiety is the above-mentioned alkyl group.
- Examples of the aryl group having 6 to 14 carbon atoms represented by R 22 include a phenyl group, a toluyl group, a dimethylphenyl group and a naphthyl group.
- R 22 is preferably a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom.
- divalent aliphatic group having 1 to 10 carbon atoms represented by Q 2 a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms is preferable.
- the carbon number of the saturated aliphatic group is preferably 1 to 8, more preferably 2 to 6, still more preferably 3 to 6, and still more preferably 4 to 6.
- the repeat number n-1 is as described above.
- the polyorganosiloxane block (A-2) represented by the above general formula (II-V) or (II-VI) uses a polyorganosiloxane raw material represented by the following general formula (5) or (6) It can be obtained by [Wherein, R 18 to R 22 , Q 2 and n-1 are as described above. ] [Wherein, n-1 is as described above. ]
- the method for producing the polyorganosiloxane is not particularly limited.
- cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopentasiloxane, and then An addition reaction of a phenolic compound (eg, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) with the ⁇ , ⁇ -dihydrogenorganopentasiloxane in the presence of a catalyst for hydrosilylation reaction is carried out Thus, a crude polyorganosiloxane can be obtained.
- a phenolic compound eg, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.
- the ⁇ , ⁇ -dihydrogenorganopolysiloxane obtained by reacting octamethylcyclotetrasiloxane and tetramethyldisiloxane in the presence of sulfuric acid (acid catalyst) in the same manner as described above, a crude polyorganosiloxane can be obtained by subjecting a phenolic compound or the like to an addition reaction in the presence of a hydrosilylation reaction catalyst.
- the ⁇ , ⁇ -dihydrogen organopolysiloxane may be used by appropriately adjusting the chain length n according to the polymerization conditions, or a commercially available ⁇ , ⁇ -dihydrogen organopolysiloxane may be used.
- a hydrosilylation catalyst what is described in Unexamined-Japanese-Patent No. 2016-098292 can be used.
- Polycarbonate oligomers can be produced by the reaction of dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, chloroform and the like.
- a carbonate precursor such as phosgene or triphosgene
- organic solvent such as methylene chloride, chlorobenzene, chloroform and the like.
- a polycarbonate oligomer using a transesterification method it can also be produced by the reaction of dihydric phenol and a carbonate precursor such as diphenyl carbonate.
- dihydric phenol As dihydric phenol, it is preferable to use dihydric phenol represented by the following general formula (viii). [Wherein, R 1 , R 2 , a, b and X are as described above. ]
- dihydric phenols represented by the above general formula (viii) include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis Bis (hydroxyphenyl) alkanes such as 4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) Cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone and the like Be These dihydric phenols may be used alone or in combination of two or more.
- bis (hydroxyphenyl) alkane-based dihydric phenol is preferable, and bisphenol A is more preferable.
- dihydric phenols other than bisphenol A for example, bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxy aryl ethers, dihydroxy diaryl sulfides, dihydroxy diaryl sulfoxides, dihydroxy diaryl sulfones, dihydroxy Diphenyls, dihydroxy diaryl fluorenes, dihydroxy diaryl adamantane etc. are mentioned. These dihydric phenols may be used alone or in combination of two or more.
- bis (hydroxyaryl) alkanes examples include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2- Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxy) Phenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy) -3,5-Dimethylphenyl) propane and 2,2-bis (4-hydroxy-3-chlorofe Nyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane
- bis (hydroxyaryl) cycloalkanes for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Examples thereof include -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane and the like.
- dihydroxy aryl ethers include 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl phenyl ether and the like.
- dihydroxydiaryl sulfides examples include 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and the like.
- dihydroxy diaryl sulfoxides examples include 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide and the like.
- dihydroxy diaryl sulfones examples include 4,4'-dihydroxy diphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone and the like.
- dihydroxydiphenyls examples include 4,4'-dihydroxydiphenyl and the like.
- dihydroxydiaryl fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like.
- dihydroxydiaryladamantanes examples include 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7- Dimethyl adamantane etc. are mentioned.
- dihydric phenols other than the above, for example, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5 And -bis (4-hydroxyphenylthio) -2,3-dioxapentane and the like.
- a termination agent can be used to adjust the molecular weight of the resulting PC-POS copolymer.
- the terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol Mention may be made of monohydric phenols. These monohydric phenols may be used alone or in combination of two or more.
- the PC-POS copolymer (A) of the present invention can be obtained by concentrating the obtained organic phase [concentrating step] and drying [drying step].
- the content of a unit represented by the following general formula (III) in the polyorganosiloxane block (A-2) is 0.1 mol% or less Is preferred.
- R 33 and R 34 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- R 31 represents 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, an arylene group having 6 to 12 carbon atoms, It shows a fluorenediyl group, an aryl alkylene group having 7 to 15 carbon atoms, and an aryl alkylidene group having 7 to 15 carbon atoms.
- R 35 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- t represents the average chain length of the polyorganosiloxane.
- the block represented by the above general formula (III) is 0.1 mol% or less, precise between the raw polyorganosiloxane used in the production of the PC-POS copolymer and the chain length of the copolymer
- the control can be performed, and a PC-POS copolymer having high flexibility and transparency aimed at can be obtained.
- a PC-POS copolymer in which the block represented by the above general formula (III) is 0.1 mol% or less.
- the block represented by the above general formula (III) can not be theoretically included from the synthesis procedure, and the content thereof is substantially 0.0 It is mol%.
- the content of the block represented by the general formula (III) in the PC-POS copolymer (A) is quantified by the peak of 13 C-NMR.
- the specific quantitative method is shown in the examples.
- the lower limit of quantification of this quantification method is less than 0.1 mol% according to the SN ratio of the baseline of the 13 C-NMR chart. In the region of less than 0.1 mol%, semi-quantitative determination is possible although quantification is impossible.
- the content of the block represented by the above general formula (III) in the PC-POS copolymer (A) contained in the molded article of the present invention specified by the aforementioned quantitative method or semi-quantitative method is more preferable Is preferably at most 0.08 mol%, more preferably at most 0.05 mol%, particularly preferably substantially 0.0 mol%.
- phosgene gas having polymerization activity is reacted with a mixture of a bisphenol monomer and a polyorganosiloxane monomer or with a polyorganosiloxane. Therefore, even if the method of adding phosgene gas and the contact time are improved to reduce the amount of block represented by the above general formula (III), contact between a plurality of polyorganosiloxane monomer molecules and phosgene gas having polymerization activity can not be avoided. It is impossible to substantially reduce the amount of block represented by the general formula (III) to 0.0% by mole.
- a bisphenol monomer and phosgene gas are reacted in advance to synthesize a bisphenol monomer or bisphenol polycarbonate oligomer having a chloroformate structure at both ends, and a chloroformate group having polymerization activity at both ends.
- a polyorganosiloxane monomer which is polymerization inactive or a bisphenol monomer which is polymerization inactive with a polymerization inactive polyorganosiloxane monomer with respect to a bisphenol monomer which has a hydroxyl group or a bisphenol polycarbonate oligomer which has a chloroformate group which has polymerization activity at both ends Can not substantially form the above general formula (III).
- Raw material pellets can be obtained by melt-kneading the PC-POS copolymer of the present invention.
- other additives may be added at the time of preparation of the raw material pellet as long as the effects of the present invention are not impaired.
- Other additives may include antioxidants, ultraviolet light absorbers, mold release agents, reinforcing materials, fillers, elastomers for improving impact resistance, dyes, pigments, antistatic agents, resins other than polycarbonate, etc.
- the addition amount can also be appropriately selected at an appropriate ratio.
- Melt-kneading is carried out by premixing with a commonly used device such as a ribbon blender or drum tumbler to obtain a Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multi-screw extruder and Conida And the like.
- mixing is normally selected suitably in the range of 240 degreeC or more and 320 degrees C or less.
- the use of an extruder, in particular a vented extruder is preferred.
- Various molded articles can be manufactured by a method or the like.
- the molding of the PC-POS copolymer of the present invention is characterized in having both excellent flexibility and transparency. The nature of each will be described in detail. As described below, some of the properties of the PC-POS copolymer are measured using a molded product, but these properties are attributable to the properties of the PC-POS copolymer itself. It is described as the property of the PC-POS copolymer.
- the PC-POS copolymer of the present invention has a durometer hardness of preferably 25 or more and 60 or less according to Type D durometer, which is measured by the method described in Examples according to JIS K6253-3: 2012.
- Durometer hardness is a parameter
- an optical member having a void structure having an undercut draft angle inside since it can be integrally molded without performing an internal cutting step, it can be suitably used for a collimator lens. Because it is excellent in transparency and flexibility, as household electrical appliances, besides substrates, light guide plates and housings for flexible displays, water and oil repellent films, optical adhesives, switch covers, heat sealing agents, water blocking materials, sealing , Connectors, adapters, smartphone covers, etc.
- Infusion bag infusion tube, syringe, baby bottle, mask, flat belt, filter part etc., as other parts, vibration control parts, robot case, drone case, shield, bulletproof shield, sports cushion, window for aircraft, resin compatibilization It can be suitably used as an agent or the like.
- the durometer hardness by the type D durometer of the PC-POS copolymer of the present invention is more preferably 30 or more, still more preferably 40 or more, more preferably 55 or less, still more preferably 50 or less.
- the preferred range of durometer hardness may vary depending on the application for which the shaped body of the present invention is used. For example, in the case of using for applications that place emphasis on flexibility, it is more preferably 28 or more, and more preferably 33 or less. In addition, in the case of using for applications in which both the flexibility and mechanical strength are important, the value is preferably 45 or more, more preferably 50 or less.
- the durometer hardness can be measured. Can be measured.
- the molding conditions in this case are the same as the molding method described in the examples.
- a raw material for obtaining such a molded object a material obtained by cutting, disassembling, breaking or the like of a molded object and a member including the molded object can be used.
- the PC-POS copolymer (A) of the present invention preferably has a total light transmittance of 75% or more at a thickness of 2 mm as measured in accordance with JIS K7361-1: 1997. Since the transparency is excellent when the total light transmittance under the above conditions is 75% or more, it can be suitably used as the above-described optical transparent member.
- the total light transmittance of the PC-POS copolymer (A) of the present invention at a thickness of 2 mm is more preferably 85% or more, still more preferably 89% or more, still more preferably 90% or more, still more preferably 91 % Or more, particularly preferably 92% or more.
- the molded object which consists of a PC-POS copolymer (A) of this invention can be used as an optical member and a transparent member, and, specifically, a flexible display, a light guide plate, a housing, a water repellent and an oil repellent film, an optical Adhesives, switch covers, heat sealing agents, water sealants, sealants, connectors, adapters, smartphone covers, lenses, glasses / sunglass parts, optical fiber parts, automotive battery cushioning materials, wiper blades, curve mirrors, side mirrors, Rearview mirror, lamp cover, bumper, window, exterior material, interior material, sound absorbing material, handle cover, sensor cover, watch part, stationery, cosmetic container, aquarium for aquatic life, shoe sole, cup, nail art, toy, simulated Food, suckers, cookers such as steamers, clothes, silicone wipes Remote control cover, umbrella, metal container lining, building material cover, door, window, glass interlayer, tent, mirror, show window case, plastic house, medical equipment case, infusion bag, infusion tube, syringe,
- Polydimethylsiloxane chain length and content rate It calculated by the integral value ratio of the methyl group of polydimethylsiloxane by NMR measurement.
- polydimethylsiloxane may be abbreviated as PDMS.
- Integral value of methylene group of allylphenol observed around 50 to 2.75 Chain length of polydimethylsiloxane (A / 6) / (B / 4)
- A Integral value of methyl group of dimethylsiloxane moiety observed around ⁇ -0.02 to 0.5
- B methylene group of eugenol observed around ⁇ 2.40 to 2.
- 70 Integral value of polydimethylsiloxane chain length (A / 6) / (B / 4)
- Viscosity Average Molecular Weight The viscosity average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and from this, the limiting viscosity [ ⁇ ⁇ ] is determined. Calculated with.
- Weight average molecular weight, molecular weight distribution Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) are measured under the following conditions using a high-speed GPC apparatus HLC-8220GPC (manufactured by Tosoh Corp.) under the following conditions: It calculated based on the general-purpose calibration curve created using the sample.
- Durometer hardness Type A Durometer hardness is measured using a rubber hardness tester ESA type (made by Elaston Ltd.), a constant pressure load device EDL-1 (made by Elastron Ltd.), JIS K 6253-3: 2012 Type A and ISO 7619 Type According to A, it measured under 1 kg load.
- Type D durometer hardness uses rubber hardness tester ESD type (made by Elaston Limited), constant pressure load device EDL-1 special type (with oil damper, made by Elastron Limited), JIS K 6253-3: 2012 Type D and ISO 7619 Type It measured based on 5 kg load according to D.
- the tubular reactor had a jacket portion, and cooling water was passed through the jacket to keep the temperature of the reaction solution below 40 ° C.
- the reaction solution leaving the tubular reactor is continuously introduced into a baffled tank reactor with an internal volume of 40 L equipped with a receding wing, and further an aqueous solution of sodium hydroxide of BPA 2.8 L / hr, 25
- the reaction was carried out by adding a mass% aqueous solution of sodium hydroxide at 0.07 L / hr, water at 17 L / hr and a 1 mass% aqueous solution of triethylamine at a flow rate of 0.64 L / hr.
- the reaction liquid which overflowed from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by leaving to stand, and the methylene chloride phase was collected.
- the polycarbonate oligomer thus obtained had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.
- aqueous sodium hydroxide solution B (BisP-AP (Honshu Chemical Industry Co., Ltd.) prepared in advance: 4.8 g (16 mmol), sodium hydroxide: 2.9 g (73 mmol), ion exchanged water: 42 mL, sodium hyposulfite (Na 2 S 2 O 4 ): 0.006 g (0.038 mmol)] was further added, and polymerization was allowed to proceed for 20 minutes.
- a methylene chloride solution of p-tert-butylphenol [PTBP: 1.5 g (10.0 mmol) dissolved in 10 mL of methylene chloride], sodium hydroxide of BPA Aqueous solution C [bisphenol A: 7.4 g (26 mmol), NaOH: 5.2 g (131 mmol) and Na 2 S 2 O 4 : 0.006 g (0.038 mmol) dissolved in 77 mL of ion-exchanged water]
- PTBP p-tert-butylphenol
- the reaction solution was transferred to a separatory funnel and allowed to stand to separate into an organic phase and an aqueous phase, and then the organic layer was transferred to another separatory funnel. This is sequentially washed with 100 mL of a 0.03 mol / L aqueous solution of NaOH and 100 mL of 0.2 mol / L hydrochloric acid, and then with ion exchange water until the conductivity in the aqueous phase after washing becomes 10 ⁇ S / m or less. Repeated. The organic layer obtained after the washing was transferred to a vat and dried overnight at 48 ° C. in an explosion-proof dryer (under nitrogen atmosphere) to obtain a sheet-like PC-POS copolymer. The sheet-like PC-POS copolymer was cut to obtain a flake-like PC-POS copolymer (a1). The details of the PC-POS copolymer are shown in Table 1-1.
- Production Example 3 The amount of allylphenol end-modified polydimethylsiloxane is 40.4 g, and as sodium hydroxide aqueous solution C, bisphenol A: 3.0 g (10 mmol), NaOH: 5.2 g (131 mmol) and Na 2 S 2 O 4 : 0 Production was carried out in the same manner as in Production Example 1 except that a solution of .006 g (0.038 mmol) dissolved in 77 mL of ion exchange water was used to obtain a PC-POS copolymer (a2). The details of the PC-POS copolymer are shown in Table 1-1.
- PC-POS copolymer (a10) The details of the PC-POS copolymer are shown in Table 1-1.
- Production Example 8 The amount of allylphenol end-modified polydimethylsiloxane was 96.0 g, and an aqueous solution of sodium hydroxide A was prepared by dissolving 4.0 g (100 mmol) of NaOH in 46 mL of ion exchanged water, as an aqueous solution of sodium hydroxide B , BisP-AP: 7.7 g (27 mmol), NaOH: 4.7 g (118 mmol) and Na 2 S 2 O 4 : 0.031 g (0.20 mmol) dissolved in 69 mL of ion exchanged water Production was carried out in the same manner as in Production Example 1 except that the aqueous sodium hydroxide solution C was not added, to obtain a PC-POS copolymer (a5). The details of the PC-POS copolymer are shown in Table 1-1.
- Production Example 9 The amount of allylphenol end-modified polydimethylsiloxane was 4.0 g, and as sodium hydroxide aqueous solution A, a solution of 1.5 g (38 mmol) of NaOH in 18 mL of ion exchanged water was used, PTBP 1.8 g (12.0 mmol) was used, and as sodium hydroxide aqueous solution C, bisphenol A: 13.2 g (45 mmol), NaOH: 6.3 g (159 mmol) and Na 2 S 2 O 4 : 0.031 g (0 Production was carried out in the same manner as in Production Example 1 except that a solution obtained by dissolving 20 mmol) in ion-exchanged water: 93 mL was used and that the aqueous sodium hydroxide solution B was not added, and a PC-POS copolymer ( I got a9). The details of the PC-POS copolymer are shown in Table 1-2.
- Production Example 10 The amount of allylphenol end-modified polydimethylsiloxane was 23.0 g, and an aqueous solution of sodium hydroxide A was prepared by dissolving 2.0 g (50.8 mmol) of NaOH in 23 mL of ion exchanged water, 1.8 g (12.0 mmol) of PTBP was used, and as sodium hydroxide aqueous solution C, bisphenol A: 11.7 g (40.4 mmol), NaOH: 5.8 g (146.0 mmol) and Na 2 S 2 O 4 Production was carried out in the same manner as Production Example 1 except that 0.031 g (0.20 mmol) of ion-exchanged water was dissolved in 85 mL, and sodium hydroxide aqueous solution B was not added. -POS copolymer (a12) was obtained. The details of the PC-POS copolymer are shown in Table 1-2.
- Production Example 13 The amount of allylphenol end-modified polydimethylsiloxane was 78.0 g, and as sodium hydroxide aqueous solution A, a solution of 3.5 g (87 mmol) of NaOH in 40 mL of ion exchanged water was used; 1.8 g (12.0 mmol) was used, and as sodium hydroxide aqueous solution C, bisphenol A: 7.5 g (26 mmol), NaOH: 4.4 g (109 mmol) and Na 2 S 2 O 4 : 0.031 g (0 Production is carried out in the same manner as in Production Example 1 except that a solution prepared by dissolving 20 mmol) in ion-exchanged water: 70 mL, and that the aqueous sodium hydroxide solution B is not added, is used as a PC-POS copolymer (a7). Got). The details of the PC-POS copolymer are shown in Table 1-2.
- a polycarbonate-polyorganosiloxane copolymer (A) having both excellent flexibility and transparency can be obtained.
- the molded object which consists of a polycarbonate polyorganosiloxane copolymer (A) of this invention can be used as an optical transparent member, Specifically, a flexible display, a light-guide plate, a housing, a water-repellent and oil-repellent film, an optical Adhesives, switch covers, heat sealing agents, water sealants, sealants, connectors, adapters, smartphone covers, lenses, glasses / sunglass parts, optical fiber parts, automotive battery cushioning materials, wiper blades, curve mirrors, side mirrors, Rearview mirror, lamp cover, bumper, window, exterior material, interior material, sound absorbing material, handle cover, sensor cover, watch part, stationery, cosmetic container, aquarium for aquatic life, shoe sole, cup, nail art, toy, simulated Utensils, suckers, cookers such as steamers, clothes, Siri Door wipes, remote control covers
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Abstract
Description
このような樹脂として、高い透明性や光学特性の面からアクリル系樹脂が広く検討されている(特許文献1)。アクリル系樹脂は透明性や柔軟性には優れるものの、機械強度や成形加工性、ハンドリング性に劣るという欠点を有する。
本発明は、優れた柔軟性と透明性との双方を有するポリカーボネート-ポリオルガノシロキサン共重合体を提供することを目的とする。
すなわち、本発明は下記[1]~[10]に関する。
(1)ポリカーボネート-ポリオルガノシロキサン共重合体(A)中の前記ポリオルガノシロキサンブロック(A-2)の含有量が40質量%を超え70質量%以下である。
(2)粘度平均分子量が10,000以上23,000以下である。
(3)前記ポリカーボネートブロック(A-1)として、下記一般式(I)中のa及びbが0であり、Xがイソプロピリデン基を示すポリカーボネートブロックを含む。
[式中、R1及びR2はそれぞれ独立に、ハロゲン原子、炭素数1~6のアルキル基又は炭素数1~6のアルコキシ基を示す。Xは、単結合、炭素数1~8のアルキレン基、炭素数2~8のアルキリデン基、炭素数5~15のシクロアルキレン基、炭素数6~12のアリーレン基、炭素数5~15のシクロアルキリデン基、フルオレンジイル基、炭素数7~15のアリールアルキレン基、炭素数7~15のアリールアルキリデン基、-S-、-SO-、-SO2-、-O-又は-CO-を示す。R3及びR4はそれぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。a及びbは、それぞれ独立に0~4の整数を示す。]
[2]前記ポリオルガノシロキサンブロック(A-2)に占める、下記一般式(III)で表される単位の含有量が0.1モル%以下である、上記[1]に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[式中、R33及びR34はそれぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。R31は炭素数1~8のアルキレン基、炭素数2~8のアルキリデン基、炭素数5~15のシクロアルキレン基、炭素数5~15のシクロアルキリデン基、炭素数6~12のアリーレン基、フルオレンジイル基、炭素数7~15のアリールアルキレン基、炭素数7~15のアリールアルキリデン基を示す。R35は水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。tはポリオルガノシロキサンの平均鎖長を示す。]
[3]前記ポリオルガノシロキサンブロック(A-2)の繰り返し数が10以上90未満である、上記[1]または[2]に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[4]前記ポリオルガノシロキサンブロック(A-2)の繰り返し数が10以上40以下である、上記[3]に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[5]分子量分布Mw/Mnが2.1以上3.9以下である、上記[1]~[4]のいずれか1つに記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[7]前記ポリオルガノシロキサンブロック(A-2)が下記一般式(II-I)~(II-III)の少なくとも1つで表される単位を含む、上記[1]~[6]のいずれか1つに記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[式中、R3~R6は、それぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示し、複数のR3~R6は、互いに同一であっても異なっていてもよい。Yは-R7O-、-R7COO-、-R7NH-、-R7NR8-、-COO-、-S-、-R7COO-R9-O-、または-R7O-R10-O-を示し、複数のYは、互いに同一であっても異なっていてもよい。前記R7は、単結合、直鎖、分岐鎖若しくは環状アルキレン基、アリール置換アルキレン基、置換または無置換のアリーレン基、またはジアリーレン基を示す。R8は、アルキル基、アルケニル基、アリール基、またはアラルキル基を示す。R9は、ジアリーレン基を示す。R10は、直鎖、分岐鎖もしくは環状アルキレン基、又はジアリーレン基を示す。βは、ジイソシアネート化合物由来の2価の基、又はジカルボン酸若しくはジカルボン酸のハロゲン化物由来の2価の基を示す。nはポリオルガノシロキサンの鎖長を示し、n-1及びpとqはそれぞれポリオルガノシロキサン単位の繰り返し数を示す1以上の整数であり、pとqの和はn-2である。]
[8]前記ポリオルガノシロキサンブロック(A-2)が下記一般式(V)で表される、上記[1]~[7]のいずれか1つに記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[式中、R3~R6及びn-1は、上記一般式(II-I)~(II-III)に記載のものと同様である。R15は、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。]
[9]JIS K 7361-1:1997に準拠して測定した2mm厚における全光線透過率が75%以上である、上記[1]~[8]のいずれか1つに記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[10]JIS K 6253-3:2012に準拠して測定される、タイプDデュロメーターによるデュロメーター硬さが25以上60以下である、上記[1]~[9]のいずれか1つに記載のポリカーボネート-ポリオルガノシロキサン共重合体。
(1)前記ポリオルガノシロキサンブロック(A-2)の含有量が40質量%を超え70質量%以下である。
(2)粘度平均分子量が10,000以上23,000以下である。
(3)前記ポリカーボネートブロック(A-1)として、前記一般式(I)中のa及びbが0であり、Xがイソプロピリデン基を示すポリカーボネートブロックを含む。
R1及びR2がそれぞれ独立して示すアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、各種ブチル基(「各種」とは、直鎖状及びあらゆる分岐鎖状のものを含むことを示し、以下同様である。)、各種ペンチル基、及び各種ヘキシル基が挙げられる。R1及びR2がそれぞれ独立して示すアルコキシ基としては、アルキル基部位が前記アルキル基である場合が挙げられる。
ポリカーボネートブロック(A-1)として、上記した(3)の要件を満たす限り、複数種のポリカーボネートブロックを含んでいてもよい。ポリカーボネートブロック(A-1)が複数種のブロックを含む場合には、上記BPAブロックと、その他のポリカーボネートブロックとの合計が100質量%となる。
上記一般式(II)中、R3又はR4がそれぞれ独立して示すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。R3又はR4がそれぞれ独立して示すアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、及び各種ヘキシル基が挙げられる。R3又はR4がそれぞれ独立して示すアルコキシ基としては、アルキル基部位が前記アルキル基である場合が挙げられる。R3又はR4がそれぞれ独立して示すアリール基としては、フェニル基、ナフチル基等が挙げられる。
R3及びR4としては、好ましくは、いずれも水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基であり、いずれもメチル基であることがより好ましい。
R3~R6としては、好ましくは、いずれも水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基または炭素数6~12のアリール基である。
一般式(II-I)、(II-II)及び/または(II-III)中のR3~R6がいずれもメチル基であることが好ましい。
(式中cは正の整数を示し、通常1~6の整数である)
R7、Ar1及びAr2が表すアリーレン基としては、フェニレン基、ナフチレン基、ビフェニレン基、アントリレン基などの環形成炭素数6~14のアリーレン基が挙げられる。これらアリーレン基は、アルコキシ基、アルキル基等の任意の置換基を有していてもよい。
R8が示すアルキル基としては炭素数1~8、好ましくは1~5の直鎖または分岐鎖のものである。アルケニル基としては、炭素数2~8、好ましくは2~5の直鎖または分岐鎖のものが挙げられる。アリール基としてはフェニル基、ナフチル基等が挙げられる。アラルキル基としては、フェニルメチル基、フェニルエチル基等が挙げられる。
R10が示す直鎖、分岐鎖もしくは環状アルキレン基は、R7と同様である。
式(II-II)中のp及びqについては、p=qであることが好ましい。
βは、ジイソシアネート化合物由来の2価の基またはジカルボン酸またはジカルボン酸のハロゲン化物由来の2価の基を示し、例えば、以下の一般式(iii)~(vii)で表される2価の基が挙げられる。
[式中、R3~R6及びnは、上記一般式(II-I)~(II-III)に記載のものと同様である。R15は、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。]
該繰り返し数は核磁気共鳴(NMR)測定により算出される。ポリオルガノシロキサンブロック(A-2)の繰り返し数を上記範囲とすることにより、優れた透明性と柔軟性とを両立することができ、成形体作製後の剥離を抑制することができる。
本発明のPC-POS共重合体(A)中のポリオルガノシロキサンブロック(A-2)の含有量は、好ましくは41質量%以上、より好ましくは45質量%以上であり、好ましくは65質量%以下、より好ましくは60質量%以下である。
粘度平均分子量(Mv)は、好ましくは12,000以上、より好ましくは14,000以上、さらに好ましくは16,000以上であり、好ましくは21,500以下、より好ましくは20,500以下、さらに好ましくは19,500以下、よりさらに好ましくは18,500以下、特に好ましくは18,000以下である。粘度平均分子量が10,000以上であれば、十分な成形品の強度を得ることができる。
粘度平均分子量(Mv)は、20℃における塩化メチレン溶液の極限粘度〔η〕を測定し、下記Schnellの式から算出した値である。
PC-POS共重合体(A)の上記分子量分布Mw/Mnは、より好ましくは2.3以上、さらに好ましくは2.4以上、よりさらに好ましくは2.5以上、よりさらに好ましくは2.7以上、特に好ましくは2.8以上であり、より好ましくは3.5以下、さらに好ましくは3.0以下、特に好ましくは2.9以下である。
得られる共重合体の透明性は、上記有機溶媒とポリカーボネートオリゴマーとの混合溶液1L中におけるポリカーボネートオリゴマーの固形分重量(g/L)が低いほど良好となるので、その下限については特に制限は無いが、PC-POS共重合体を効率良く製造する観点からは、好ましくは20g/L以上、より好ましくは、30g/L以上、さらに好ましくは40g/L以上である。
Zは、水素原子またはハロゲン原子を示し、複数のZは、互いに同一であっても異なっていてもよい。
これらの中でも、重合の容易さの観点においては、上記一般式(1-1)で表されるフェノール変性ポリオルガノシロキサンが好ましい。入手の容易さの観点においては、上記一般式(1-2)で表される化合物中の一種であるα,ω-ビス[3-(o-ヒドロキシフェニル)プロピル]ポリジメチルシロキサン、上記一般式(1-3)で表される化合物中の一種であるα,ω-ビス[3-(4-ヒドロキシ-3-メトキシフェニル)プロピル]ポリジメチルシロキサンが好ましい。
上記(4)をポリオルガノシロキサン原料として用いた場合には、ポリオルガノシロキサンブロック(A-2)は下記一般式(II-IV)で表わされる単位を有することが好ましい。
[式中、R18~R21はそれぞれ独立に水素原子又は炭素数1~13のアルキル基である。R22は炭素数1~6のアルキル基、水素原子、ハロゲン原子、ヒドロキシ基、炭素数1~6のアルコキシ基、又は炭素数6~14のアリール基である。Q2は炭素数1~10の2価の脂肪族基である。n-1はポリオルガノシロキサンブロックの繰り返し数を示し、その範囲は上記した通りである]
上記の中でも、R22は水素原子、又は炭素数1~6のアルコキシ基が好ましく、水素原子又は炭素数1~3のアルコキシ基がより好ましく、水素原子がさらに好ましい。
[式中、R18~R22、Q2、及びn-1は上記した通りである。]
[式中、n-1は上記した通りである。]
これらの中でも、ビス(ヒドロキシフェニル)アルカン系二価フェノールが好ましく、ビスフェノールAがより好ましい。二価フェノールとしてビスフェノールAを用いた場合、上記一般式(i)において、Xがイソプロピリデン基であり、且つa=b=0のPC-POS共重合体となる。
具体的には、上記した界面重合法を採用することにより、上記一般式(III)で表されるブロックが0.1モル%以下となるPC-POS共重合体を得ることができる。本発明のPC-POS共重合体(A)中には上記一般式(III)で表されるブロックは、合成手順からは理論的に含まれ得ず、その含有量は実質的に0.0モル%である。
前述の定量方法、半定量方法により特定した、本発明の成形体に含まれるPC-POS共重合体(A)中での上記一般式(III)で表されるブロックの含有量は、より好ましくは0.08モル%以下、さらに好ましくは0.05モル%以下、特に好ましくは実質的に0.0モル%である。
一方、本発明の合成方法では、予め、ビスフェノールモノマーとホスゲンガスとを反応させて、両末端がクロロホーメート構造であるビスフェノールモノマーもしくはビスフェノールポリカーボネートオリゴマーを合成し、両末端に重合活性のクロロホーメート基を有するビスフェノールモノマー、もしくは両末端に重合活性のクロロホーメート基を有するビスフェノールポリカーボネートオリゴマーに対して、重合不活性のポリオルガノシロキサンモノマー、もしくは重合不活性のポリオルガノシロキサンモノマーと重合不活性のビスフェノールモノマーを反応させるため、上記式一般式(III)は実質的に生成し得ない。
上記の溶融混練したポリカーボネート-ポリオルガノシロキサン共重合体、又は得られたペレットを原料として、射出成形法、射出圧縮成形法、押出成形法、ブロー成形法、プレス成形法、真空成形法及び発泡成形法等により各種成形体を製造することができる。
デュロメーター硬さとは、押込み硬さを示す指標である。ある程度の機械強度を維持しつつ高い柔軟性を有する成形体とするために、タイプDデュロメーター硬さを有することが好ましい。本発明のPC-POS共重合体は柔軟性に優れるため、パッキン部材を介することなく照明カバーとして用いること、及び複雑な形状のライトガイドに対応すること等を可能にし、施工容易性を飛躍的に高めることができる。さらに、内部にアンダーカット抜き勾配角度を有する空隙構造を持つ光学部材の場合でも、内部切削工程を実施することなく一体成形が可能であるため、コリメーターレンズに好適に用いることができる。透明性かつ柔軟性に優れることから、家電関係として、フレキシブルディスプレイの基板や導光板、ハウジングの他、撥水・撥油フィルム、光学粘着剤、スイッチカバー、ヒートシール剤、止水材、封止剤、コネクター、アダプター、スマートフォンカバー等、光学用途として、レンズ、眼鏡・サングラスパーツ、光ファイバーパーツ、自動車関係では、車載電池用クッション材、ワイパーブレード、カーブミラー、サイドミラー、バックミラー、ランプカバー、バンパー、ウィンドウ、ガラス中間層、外装材、内装材、吸音材、ハンドルカバー、センサーカバー等、日用品類として、時計パーツ、文房具、化粧品容器、水生生物飼育用水槽、靴底、コップ、ネイルアート、おもちゃ、疑似餌、吸盤、スチーマー等の調理器具、衣服、シリコーン拭き取りシート、リモコンカバー、傘、金属容器内張り等、建材関係では、建材カバー、扉、窓、ガラス中間層、テント、鏡、ショーウィンドウケース、ビニールハウス等、医療関係では、メディカル機器筐体、輸液バック、輸液チューブ、注射器、哺乳瓶、マスク、面帯、フィルターパーツ等、その他として、制振パーツ、ロボット筐体、ドローン筐体、盾、防弾シールド、スポーツクッション、飛行機用窓、樹脂相溶化剤等に好適に用いることができる。
本願の成形体を使用する用途によっては、デュロメーター硬さの好ましい範囲が変化することもある。例えば、柔軟性を重視する用途に使用する場合は28以上であることがより好ましく、33以下であることがより好ましい。その他、柔軟性及び機械的強度の両方を重視する用途に使用する場合は、45以上であることがより好ましく、50以下であることがより好ましい。
そのような成形体を得るための原料としては、成形体及び成形体を含む部材を切削、分解、破壊等して得られたものを用いることができる。
本発明のPC-POS共重合体(A)の、2mm厚における全光線透過率は、より好ましくは85%以上、さらに好ましくは89%以上、よりさらに好ましくは90%以上、よりさらに好ましくは91%以上、特に好ましくは92%以上である。
NMR測定によって、ポリジメチルシロキサンのメチル基の積分値比により算出した。なお、本明細書においては、ポリジメチルシロキサンをPDMSと略記することがある。
<ポリジメチルシロキサンの鎖長の定量方法>
1H-NMR測定条件
NMR装置:(株)JEOL RESONANCE製 ECA500
プローブ:50TH5AT/FG2
観測範囲:-5~15ppm
観測中心:5ppm
パルス繰り返し時間:9秒
パルス幅:45°
NMR試料管:5φ
サンプル量:30~40mg
溶媒:重クロロホルム
測定温度:室温
積算回数:256回
アリルフェノール末端ポリジメチルシロキサンの場合
A:δ-0.02~0.5付近に観測されるジメチルシロキサン部のメチル基の積分値
B:δ2.50~2.75付近に観測されるアリルフェノールのメチレン基の積分値
ポリジメチルシロキサンの鎖長=(A/6)/(B/4)
オイゲノール末端ポリジメチルシロキサンの場合
A:δ-0.02~0.5付近に観測されるジメチルシロキサン部のメチル基の積分値
B:δ2.40~2.70付近に観測されるオイゲノールのメチレン基の積分値
ポリジメチルシロキサンの鎖長=(A/6)/(B/4)
アリルフェノール末端ポリジメチルシロキサンを共重合したPTBP末端ポリカーボネート中のポリジメチルシロキサン共重合量の定量方法
NMR装置:(株)JEOL RESONANCE製 ECA500
プローブ:50TH5AT/FG2
観測範囲:-5~15ppm
観測中心:5ppm
パルス繰り返し時間:9秒
パルス幅:45°
積算回数:256回
NMR試料管:5φ
サンプル量:30~40mg
溶媒:重クロロホルム
測定温度:室温
A:δ1.5~1.9付近に観測されるBPA部のメチル基の積分値
B:δ-0.02~0.3付近に観測されるジメチルシロキサン部のメチル基の積分値
C:δ1.2~1.4付近に観測されるp-tert-ブチルフェニル部のブチル基の積分値
a=A/6
b=B/6
c=C/9
T=a+b+c
f=a/T×100
g=b/T×100
h=c/T×100
TW=f×254+g×74.1+h×149
PDMS(wt%)=g×74.1/TW×100
13C-NMR測定条件
NMR装置:(株)JEOL RESONANCE製 ECA500
プローブ:C5HPD/FGプローブ
観測範囲:-25~225ppm
観測中心:100ppm
パルス繰り返し時間:4秒
パルス幅:45°
NMR試料管:10φ
サンプル量:250~300mg
溶媒:重クロロホルム
測定温度:室温
積算回数:1万回
本定量方法の定量下限は、13C-NMRのチャートのベースラインのSN比により0.1mol%未満と算出された。
[上記式中、R1,R2,R31~R35,X,a,b及びtは上記した通りである]
重量平均分子量(Mw)、分子量分布(Mw/Mn)は、高速GPC装置 HLC―8220GPC(東ソー株式会社製)を用いて、以下の条件で測定し、分子量標準試料を用いて作成した汎用較正曲線に基づき算出した。
カラム温度:40℃
カラム:TSK―GEL GHXL―L、TSK―GEL G4000HXL、TSK―GEL G2000HXL(東ソー株式会社製)
移動相溶媒:テトラヒドロフラン
流速:1.0ml/分
検出器:RI
注入濃度:10mg/10ml
注入量:0.1ml
分子量標準試料:ポリカーボネート18,050(出光興産株式会社製、分子量誤差±5%/17148~18,953)、ポリカーボネート18,100(出光興産株式会社製、分子量誤差±5%/17,200~19,100)
タイプAデュロメーター硬さは、ゴム硬度計ESA型(有限会社エラストロン製)、定圧荷重器EDL―1(有限会社エラストロン製)を用い、JISK 6253-3:2012 タイプAおよびISO7619Type Aに準拠して、1kg荷重下において測定した。
タイプDデュロメーター硬さは、ゴム硬度計ESD型(有限会社エラストロン製)、定圧荷重器EDL-1特型(オイルダンパー付、有限会社エラストロン製)を用い、JISK 6253-3:2012 タイプDおよびISO7619Type Dに準拠して5kg荷重下において測定した。
ヘイズメーターNDH 5000(日本電色工業株式会社製)を用い、JISK 7361-1:1997に準拠して、2mm厚にて測定した。
5.6質量%の水酸化ナトリウム水溶液に、ビスフェノールA(BPA)(後から溶解する)に対して2000ppmの亜二チオン酸ナトリウムを加えた。これにBPA濃度が13.5質量%となるようにBPAを溶解し、BPAの水酸化ナトリウム水溶液を調製した。このBPAの水酸化ナトリウム水溶液を40L/hr、塩化メチレンを15L/hr、及びホスゲンを4.0kg/hrの流量で内径6mm、管長30mの管型反応器に連続的に通した。管型反応器はジャケット部分を有しており、ジャケットに冷却水を通して反応液の温度を40℃以下に保った。管型反応器を出た反応液を、後退翼を備えた内容積40Lのバッフル付き槽型反応器へ連続的に導入し、ここにさらにBPAの水酸化ナトリウム水溶液を2.8L/hr、25質量%の水酸化ナトリウム水溶液を0.07L/hr、水を17L/hr、1質量%のトリエチルアミン水溶液を0.64L/hrの流量で添加して反応を行なった。槽型反応器から溢れ出る反応液を連続的に抜き出し、静置することで水相を分離除去し、塩化メチレン相を採取した。
このようにして得られたポリカーボネートオリゴマーは濃度341g/L、クロロホーメート基濃度0.71mol/Lであった。
バッフル板及び撹拌翼付のメカニカルスターラーを備えた1Lのセパラブルフラスコに、上記の通り製造したポリカーボネートオリゴマー溶液(PCO)185mL、塩化メチレン445mL、平均鎖長n=37のアリルフェノール末端変性ポリジメチルシロキサン30.3g、及びトリエチルアミン(TEA)0.104mL(0.75mmol)を仕込み、攪拌下でここに予め調製した水酸化ナトリウム水溶液A(NaOHaq)(水酸化ナトリウム1.9g(47mmol),イオン交換水22mL)を加え、20分間ポリカーボネートオリゴマーとアリルフェノール末端変性PDMSの反応を行った。次いで、予め調製した水酸化ナトリウム水溶液B[BisP-AP(本州化学工業株式会社製):4.8g(16mmol)、水酸化ナトリウム:2.9g(73mmol)、イオン交換水:42mL、次亜硫酸ナトリウム(Na2S2O4):0.006g(0.038mmol)]をさらに加えて、20分間重合を進めた。
得られた重合液に、p-tert-ブチルフェノール(PTBP:DIC株式会社製)の塩化メチレン溶液[PTBP:1.5g(10.0mmol)を塩化メチレン10mLに溶解したもの]、BPAの水酸化ナトリウム水溶液C[ビスフェノールA:7.4g(26mmol)、NaOH:5.2g(131mmol)とNa2S2O4:0.006g(0.038mmol)とをイオン交換水77mLに溶解されたもの]を添加し20分間重合反応を実施した。
重合終了後、反応液を分液漏斗に移し静置し、有機相と水相とに分離させた後、有機層を別の分液漏斗に移した。ここに、0.03mol/LのNaOH水溶液100mL、0.2mol/Lの塩酸100mLで順次洗浄し、次いで洗浄後の水相中の電気伝導度が10μS/m以下になるまでイオン交換水で洗浄を繰り返した。
洗浄後に得られた有機層をバットに移し、防爆乾燥機(窒素雰囲気下)にて48℃で一晩乾燥し、シート状のPC-POS共重合体を得た。このシート状のPC-POS共重合体を裁断することにより、フレーク状のPC-POS共重合体(a1)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を40.4gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:1.9g(47mmol)をイオン交換水:22mLに溶解させたもの、水酸化ナトリウム水溶液Bとして、BisP-B:4.8g(20mmol)、NaOH:2.9g(73mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:42mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Cとして、BPA:3g(10mmol)、NaOH:5.2g(131mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:77mLに溶解させたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a6)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサン量を40.4gとしたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:3.0g(10mmol)、NaOH:5.2g(131mmol)及びNa2S2O4:0.006g(0.038mmol)をイオン交換水:77mLに溶解させたものを用いたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a2)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンとして、平均鎖長n=23のアリルフェノール末端変性ポリジメチルシロキサンを43.0g用いたこと、水酸化ナトリウム水溶液Aとして、NaOH:3.7g(94mmol)をイオン交換水:43mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bとして、BisP-AP(本州化学工業株式会社製):5.5g(19mmol)、NaOH:2.3g(57mmol)、イオン交換水:33mL、Na2S2O4:0.031g(0.196mmol)の混合物を用いたこと、BPAの水酸化ナトリウム水溶液Cとして、ビスフェノールA:2.5g(8.7mmol)、NaOH:1.9g(46.3mmol)及びNa2S2O4:0.031g(0.196mmol)をイオン交換水:27mLに溶解させたものを用いたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a10)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンとして、平均鎖長n=63のアリルフェノール末端変性ポリジメチルシロキサンを46.0g用いたこと、水酸化ナトリウム水溶液Aとして、NaOH:2.2g(55.9mmol)をイオン交換水:26mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bとして、BisP-AP(本州化学工業株式会社製):5.8g(20mmol)、NaOH:2.4g(60mmol)、イオン交換水:35mL、Na2S2O4:0.031g(0.196mmol)の混合物用いたこと、BPAの水酸化ナトリウム水溶液Cとして、ビスフェノールA:6.6g(22.6mmol)、NaOH:3.2g(80.9mmol)及びNa2S2O4:0.031g(0.196mmol)をイオン交換水:47mLに溶解させたものを用いたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a14)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサン量を62.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:3.1g(77mmol)をイオン交換水:35mLを溶解させたもの、水酸化ナトリウム水溶液Bとして、BisP-AP:6.0g(21mmol)、NaOH:2.5g(62mmol)及びNa2S2O4:0.031g(0.20mmol)イオン交換水:36mLに溶解させたもの、水酸化ナトリウム水溶液Cとして、ビスフェノールA:4.0g(14mmol)、NaOH:2.3g(58mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:34mLに溶解させたものを用いたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a3)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を77.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:3.5g(87mmol)をイオン交換水:40mLに溶解させたもの、水酸化ナトリウム水溶液Bとして、BisP-AP:6.0g(21mmol)、NaOH:2.5g(62mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:36mLに溶解させたもの、水酸化ナトリウム水溶液Cとして、ビスフェノールA:2.9g(10mmol)、NaOH:1.9g(48mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:28mLに溶解させたものを用いたこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a4)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を96.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:4.0g(100mmol)をイオン交換水:46mLに溶解させたもの、水酸化ナトリウム水溶液Bとして、BisP-AP:7.7g(27mmol)、NaOH:4.7g(118mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:69mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Cを加えないこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a5)を得た。PC-POS共重合体の詳細を表1-1に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を4.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:1.5g(38mmol)をイオン交換水:18mLに溶解させたものを用いたこと、PTBPを1.8g(12.0mmol)用いたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:13.2g(45mmol)、NaOH:6.3g(159mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:93mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bを投入しなかったこと以外は、製造例1と同様に製造を行い、PC-POS共重合体(a9)を得た。PC-POS共重合体の詳細を表1-2に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を23.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:2.0g(50.8mmol)をイオン交換水:23mLに溶解させたものを用いたこと、PTBPを1.8g(12.0mmol)用いたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:11.7g(40.4mmol)、NaOH:5.8g(146.0mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:85mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bを投入しなかったこと以外は、製造例1と同様に製造を行い、PC-POS共重合体(a12)を得た。PC-POS共重合体の詳細を表1-2に示す。
アリルフェノール末端変性ポリジメチルシロキサンとして、平均鎖長n=63のアリルフェノール末端変性ポリジメチルシロキサンを30.0gと用いたこと、水酸化ナトリウム水溶液Aとして、NaOH:1.8g(45mmol)をイオン交換水:21mLに溶解させたものを用いたこと、PTBPを1.8g(12.0mmol)用いたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:12.3g(43mmol)、NaOH:6.1g(151mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:89mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bを投入しなかったこと以外は、製造例1と同様に製造を行い、PC-POS共重合体(a8)を得た。PC-POS共重合体の詳細を表1-2に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を55gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:2.9g(72.1mmol)をイオン交換水:33mLに溶解させたものを用いたこと、PTBPを1.8g(12.0mmol)用いたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:9.3g(32.0mmol)、NaOH:5.0g(124.7mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:73mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bを投入しなかったこと以外は、製造例1と同様に製造を行い、PC-POS共重合体(a13)を得た。PC-POS共重合体の詳細を表1-2に示す。
アリルフェノール末端変性ポリジメチルシロキサンの量を78.0gとしたこと、水酸化ナトリウム水溶液Aとして、NaOH:3.5g(87mmol)をイオン交換水:40mLに溶解させたものを用いたこと、PTBPを1.8g(12.0mmol)用いたこと、水酸化ナトリウム水溶液Cとして、ビスフェノールA:7.5g(26mmol)、NaOH:4.4g(109mmol)及びNa2S2O4:0.031g(0.20mmol)をイオン交換水:70mLに溶解させたものを用いたこと、水酸化ナトリウム水溶液Bを投入しなかったこと以外は製造例1と同様に製造を行い、PC-POS共重合体(a7)を得た。PC-POS共重合体の詳細を表1-2に示す。
各製造例で得られたPC-POS共重合体を、真空プレス機(井元製作所製、手動油圧真空加熱プレス機)を用いて成形した。縦寸法5cm×横寸法5cm×厚さ2mmの金型に樹脂を7.0g入れ、樹脂に接する面を鏡面加工されたアルミ板で挟み、真空プレス機に入れ、真空プレスの槽内を大気圧に対し、-0.1MPa以下まで減圧した。その後、表2-1及び表2-2に記載の成形温度になるまで加熱した。成形温度に達した後、プレス圧力を2MPaにしてから2分間加熱した。続いて、3分間かけてプレス圧力を上げ、5分間、15MPaを維持して成形を行った。成形後、大気圧に戻した後に成形体を取り出し、室温になるまで冷却した。その後、鏡面アルミ板から剥し、縦寸法5cm×横寸法5cm×厚さ2mmの測定用サンプルを得た。PC-POS共重合体の評価結果を表2-1および表2-2に示す。
Claims (10)
- 下記一般式(I)で表される繰り返し単位からなるポリカーボネートブロック(A-1)及び下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロック(A-2)を含むポリカーボネート-ポリオルガノシロキサン共重合体(A)であって、以下の要件(1)~(3)を満たすことを特徴とする、ポリカーボネート-ポリオルガノシロキサン共重合体。
(1)ポリカーボネート-ポリオルガノシロキサン共重合体(A)中の前記ポリオルガノシロキサンブロック(A-2)の含有量が40質量%を超え70質量%以下である。
(2)粘度平均分子量が10,000以上23,000以下である。
(3)前記ポリカーボネートブロック(A-1)として、下記一般式(I)中のa及びbが0であり、Xがイソプロピリデン基を示すポリカーボネートブロックを含む。
[式中、R1及びR2はそれぞれ独立に、ハロゲン原子、炭素数1~6のアルキル基又は炭素数1~6のアルコキシ基を示す。Xは、単結合、炭素数1~8のアルキレン基、炭素数2~8のアルキリデン基、炭素数5~15のシクロアルキレン基、炭素数6~12のアリーレン基、炭素数5~15のシクロアルキリデン基、フルオレンジイル基、炭素数7~15のアリールアルキレン基、炭素数7~15のアリールアルキリデン基、-S-、-SO-、-SO2-、-O-又は-CO-を示す。R3及びR4はそれぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。a及びbは、それぞれ独立に0~4の整数を示す。] - 前記ポリオルガノシロキサンブロック(A-2)に占める、下記一般式(III)で表される単位の含有量が0.1モル%以下である、請求項1に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[式中、R33及びR34はそれぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。R31は炭素数1~8のアルキレン基、炭素数2~8のアルキリデン基、炭素数5~15のシクロアルキレン基、炭素数5~15のシクロアルキリデン基、炭素数6~12のアリーレン基、フルオレンジイル基、炭素数7~15のアリールアルキレン基、炭素数7~15のアリールアルキリデン基を示す。R35は水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示す。tはポリオルガノシロキサンの平均鎖長を示す。] - 前記ポリオルガノシロキサンブロック(A-2)の繰り返し数が10以上90未満である、請求項1または2に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
- 前記ポリオルガノシロキサンブロック(A-2)の繰り返し数が10以上40以下である、請求項3に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
- 分子量分布Mw/Mnが2.1以上3.9以下である、請求項1~4のいずれか一項に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
- 重量平均分子量が40,000以下である、請求項1~5のいずれか一項に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
- 前記ポリオルガノシロキサンブロック(A-2)が下記一般式(II-I)~(II-III)の少なくとも1つで表される単位を含む、請求項1~6のいずれか一項に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
[式中、R3~R6は、それぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を示し、複数のR3~R6は、互いに同一であっても異なっていてもよい。Yは-R7O-、-R7COO-、-R7NH-、-R7NR8-、-COO-、-S-、-R7COO-R9-O-、または-R7O-R10-O-を示し、複数のYは、互いに同一であっても異なっていてもよい。前記R7は、単結合、直鎖、分岐鎖若しくは環状アルキレン基、アリール置換アルキレン基、置換または無置換のアリーレン基、またはジアリーレン基を示す。R8は、アルキル基、アルケニル基、アリール基、またはアラルキル基を示す。R9は、ジアリーレン基を示す。R10は、直鎖、分岐鎖もしくは環状アルキレン基、又はジアリーレン基を示す。βは、ジイソシアネート化合物由来の2価の基、又はジカルボン酸若しくはジカルボン酸のハロゲン化物由来の2価の基を示す。nはポリオルガノシロキサンの鎖長を示し、n-1及びpとqはそれぞれポリオルガノシロキサン単位の繰り返し数を示す1以上の整数であり、pとqの和はn-2である。] - JIS K 7361-1:1997に準拠して測定した、2mm厚における全光線透過率が75%以上である、請求項1~8のいずれか一項に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
- JIS K 6253-3:2012に準拠して測定される、タイプDデュロメーターによるデュロメーター硬さが25以上60以下である、請求項1~9のいずれか一項に記載のポリカーボネート-ポリオルガノシロキサン共重合体。
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US20220169788A1 (en) * | 2019-03-22 | 2022-06-02 | Mitsubishi Gas Chemical Company, Inc. | Methods for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded body |
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