WO2023171578A1 - 熱可塑性樹脂及びその製造方法、熱可塑性樹脂組成物、及び成形体 - Google Patents

熱可塑性樹脂及びその製造方法、熱可塑性樹脂組成物、及び成形体 Download PDF

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WO2023171578A1
WO2023171578A1 PCT/JP2023/008159 JP2023008159W WO2023171578A1 WO 2023171578 A1 WO2023171578 A1 WO 2023171578A1 JP 2023008159 W JP2023008159 W JP 2023008159W WO 2023171578 A1 WO2023171578 A1 WO 2023171578A1
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thermoplastic resin
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French (fr)
Japanese (ja)
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康平 釜谷
宣人 秋元
行宏 瀬谷
大輔 田口
和良 上等
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三菱瓦斯化学株式会社
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    • 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
    • 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
    • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to thermoplastic resins, particularly polycarbonate-polysilyl ether resins, and further relates to methods for producing thermoplastic resins, compositions containing thermoplastic resins, and the like.
  • Polycarbonate resins having an isosorbide (ISB) skeleton are known to have high transparency, scratch resistance, and impact resistance. Furthermore, ISB is a plant-derived raw material, and plastics using such resin raw materials are attracting attention as bioplastics.
  • polycarbonate resin as a homopolymer having an ISB skeleton has a high glass transition temperature, tends to be hard and brittle, and has problems in moldability. Therefore, in order to solve the problem of moldability, for example, a copolymer which is a combination of ISB and an alicyclic diol such as spiroglycol has been developed (Patent Documents 1 and 2).
  • copolymers of ISB and spiroglycol tend not to fully exhibit the above-mentioned excellent properties observed in ISB homopolymers.
  • alicyclic diols such as ISB and SPG are usually polymerized at high temperatures over a long period of time, so deterioration reactions may occur. There were problems in that by-products were likely to be produced and the resulting resin would be colored. Furthermore, such copolymers tended to have poor chemical resistance.
  • the main object of the present invention is to provide a thermoplastic resin, particularly a polycarbonate-polysilyl ether resin, which has excellent moldability, good hue, and high chemical resistance.
  • the present invention has been made in view of the problems of the prior art described above, and provides a thermoplastic resin etc. that has excellent moldability.
  • the thermoplastic resin of the present invention contains a specific structural unit, has a low glass transition temperature, high fluidity when melted, etc., and is also excellent in hue, chemical resistance, etc.
  • Rs 1 and Rs 2 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 6 to 30 carbon atoms which may have a substituent.
  • thermoplastic resin according to [1] above wherein the total content of the structural unit (A) and the structural unit (B) in all structural units of the thermoplastic resin is 50 mol% or more. .
  • thermoplastic resin according to [2] above which contains only the structural unit (A) and the structural unit (B) as structural units.
  • thermoplastic resin according to [1] or [2] above further comprising a structural unit (Z) derived from a monomer represented by any of the following general formulas (I 1 ) to (I 6 ).
  • R 1 and R 2 are independently -(CR 5 R 6 ) q1 - or -(-O-(CR 5 R 6 ) q2 -) q3 - (wherein R 5 and R 6 are independently , H or a C 1-6 alkyl group, q1 represents an integer of 0 or more and 10 or less, q2 represents an integer of 1 or more and 10 or less, q3 represents an integer of 1 or more and 10 or less, q1 or When q2 is an integer of 2 or more, a plurality of R 5 or R 6 may be the same or different from each other), R 3 and R 4 are independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, a C 1-20 aliphatic hydrocarbon group, a C 1-20 alkoxyl group, a C 3- 20 cycloalkyl group, C 6-20 aromatic hydrocarbon group, C 7-20 aralkyl group, C 6-20 aromatic hydro
  • R 9 and R 10 independently represent H or a C 1-6 alkyl group, and when r1 is an integer of 2 or more, multiple R 9 or R 10 may be the same or different from each other.
  • R 11 to R 18 are independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, a C 1-20 aliphatic hydrocarbon group which may have a substituent ⁇ , a substituted Represents a C 1-20 alkoxyl group that may have a group ⁇ or a C 6-12 aromatic hydrocarbon group that may have a substituent ⁇ , R 19 represents a C 1-9 alkylene group which may have a substituent ⁇ , r1 represents an integer of 1 or more and 20 or less, r2 represents an integer of 1 or more and 500 or less.
  • the substituent ⁇ is one or more halogeno groups selected from the group consisting of a C 1-6 alkoxyl group, a C 1-7 acyl group, chloro, bromo, and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group.
  • one or more substituents selected from The substituent ⁇ is one or more halogeno groups, amino groups, and nitro groups selected from the group consisting of C 1-6 alkyl groups, C 1-6 alkoxyl groups, C 1-7 acyl groups, chloro, bromo, and iodo.
  • R 20 and R 21 are independently -(CR 5 R 6 ) m1 - or -(-O-(CR 5 R 6 ) m2 -) m3 - (wherein R 5 and R 6 have the same meanings as above)
  • m 1 represents an integer of 1 or more and 10 or less
  • m 2 represents an integer of 1 or more and 10 or less
  • m 3 represents an integer of 1 or more and 10 or less
  • m 1 or m 2 represents an integer of 1 or more and 10 or less.
  • X 4 represents a divalent group containing one or more hydrocarbon rings or heterocycles, However, isosorbide is excluded from the monomers represented by formula (I 4 ).
  • HO-R 1 -X 5 -R 2 -OH (I 5 ) [In formula (I 5 ), R 1 and R 2 have the same meanings as above, and X 5 represents a divalent saturated heterocyclic group.
  • X 6 represents a C 1-10 alkylene group, n represents an integer of 13 or more and 50 or less.
  • thermoplastic resin according to any one of [1] to [4] above which has a glass transition temperature of 50 to 160°C.
  • thermoplastic resin according to any one of [1] to [5] above which has a Q value of 3 to 120 (10 ⁇ 2 ml/sec) measured under the conditions of 240° C. and a load of 160 kg.
  • Q value 3 to 120 (10 ⁇ 2 ml/sec) measured under the conditions of 240° C. and a load of 160 kg.
  • the thermoplastic resin according to any one of [1] to [6] above which has a YI value of 15.0 or less as measured according to JIS K 7373.
  • the thermoplastic resin according to any one of [1] to [7] above having a Si content of 0.4 to 10.0% by mass.
  • thermoplastic resin composition comprising the thermoplastic resin according to any one of [1] to [8] above and a cyclic body represented by the following general formula (K).
  • a thermoplastic resin composition comprising the thermoplastic resin according to any one of [1] to [9] above and an antioxidant.
  • thermoplastic resin according to any one of [1] to [8] above or the thermoplastic resin composition according to any one of [9] and [10] above.
  • thermoplastic resin composition according to any one of [9] and [10] above.
  • thermoplastic resin according to any one of [1] to [8] above, (i) an isosorbide compound represented by the following formula (3), (ii) A monomer compound containing a carbonate compound as a source of a carbonate bonding site in the structural unit (A), and (iii) a silane compound as a source of a silyl ether bonding site in the structural unit (B) is subjected to a polymerization reaction.
  • a manufacturing method comprising adding an antioxidant to the monomer compound before the polymerization reaction.
  • the antioxidant includes a phosphite antioxidant.
  • the molar ratio of the (i) isosorbide compound to the total amount of the (ii) carbonate compound and the (iii) silane compound used in the polymerization step is 25/75 to 60/40.
  • thermoplastic resin according to any one of [14] to [17] above, wherein the carbonate compound (ii) contains any one of dialkyl carbonate, monoalkylmonophenyl carbonate, and diphenyl carbonate.
  • the silane compound (iii) is A diaryloxysilane compound containing at least one of dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane, and Any one of [14] to [18] above, containing at least one selected from dialkoxysilane compounds containing at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane.
  • the method for producing a thermoplastic resin described in .
  • thermoplastic resin having excellent moldability, hue, chemical resistance, etc.
  • thermoplastic resin polycarbonate-polysilyl ether resin
  • the thermoplastic resin of the present invention has a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2).
  • the structural units (A) and (B) are preferably main components in the main chain of the thermoplastic resin.
  • the structural unit (A) corresponds to a carbonate moiety
  • the structural unit (B) corresponds to a silyl ether moiety
  • the thermoplastic of the present invention having these structural units
  • the resin can also be said to be a polycarbonate-polysilyl ether resin (polycarbonate-polysilyl ether copolymer).
  • the structural units (A) and (B) may each be a structural unit derived from isosorbide, isomannide, or isoidet. That is, the structural units (A) and (B) are both formed using isosorbide (1,4:3,6-dianhydro-D-sorbitol), isomannide, or isoidet represented by the following formula (3a).
  • the isosorbide compound represented by the general formula (3), which is the structural unit to be obtained, can be used as a raw material for the structural units (A) and (B). Therefore, the structural unit derived from isosorbide includes a structural unit derived from any one of isosorbide compounds such as isosorbide, isomannide, and isoidet.
  • Rs 1 and Rs 2 are each independently an alkyl group having a total number of carbon atoms of 1 to 20 which may have a substituent, or an alkyl group having a total number of carbon atoms which may have a substituent. 6 to 30 aryl groups.
  • the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and the total number of carbon atoms is preferably 1 to 10. is particularly preferably 1 or 2.
  • the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, It is particularly preferred that the total number of carbon atoms is 6 to 8.
  • Examples of the substituents for Rs 1 and Rs 2 above include, each independently, a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, etc. .
  • Preferred specific examples of Rs 1 and Rs 2 include a methyl group, a phenyl group, a vinyl group, and a propyl group, with a methyl group being more preferred.
  • the structural unit (B) derived from isosorbide has a structure represented by the following formula (2a).
  • the structural unit (B) in which Rs 1 and Rs 2 are methyl groups is, for example, the following formula (2-1a) or the following formula (2-1) derived from dimethyldiphenoxysilane, as detailed later. has the structure represented.
  • the molar ratio of the structural unit (A) and the structural unit (B), that is, the molar ratio of the carbonate site and the silyl ether site (A):(B) is 30/70 to 99/1.
  • the total content of the structural unit (A) and the structural unit (B) in the thermoplastic resin that is, the total number of moles of the structural unit (A) and the structural unit (B) in the number of moles of all the structural units of the thermoplastic resin.
  • the proportion is, for example, 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, or even more preferably 90 mol% or more.
  • the thermoplastic resin particularly preferably substantially or completely contains only the structural unit (A) and the structural unit (B) as structural units.
  • thermoplastic resins containing structural units derived from isosorbide as a main component are expected to have excellent moldability, color, chemical resistance, etc., as well as excellent mechanical strength.
  • polycarbonate resins mainly contain structural units derived from linear diols or monocyclic/alicyclic alkylene diols (e.g. carbonate structural units)
  • polycarbonate resins mainly contain structural units derived from isosorbide.
  • Thermoplastic resins have the above-mentioned excellent properties.
  • thermoplastic resin may contain structural units (arbitrary structural units (Z)) other than the structural units (A) and (B), which can be said to be the main components constituting the main chain.
  • structural units (Z)) other than the structural units (A) and (B), which can be said to be the main components constituting the main chain.
  • it is a structural unit derived from the following diol compound.
  • thermoplastic resin examples include those derived from diol compounds represented by any of the following formulas (I 1 ) to (I 6 ). These diol compounds may be abbreviated as diol compounds (I 1 ) to (I 6 ), respectively.
  • the diol compound (I 1 ) is represented by the following formula (I 1 ).
  • R 1 and R 2 are independently -(CR 5 R 6 ) q1 - or -(-O-(CR 5 R 6 ) q2 -) q3 - (wherein R 5 and R 6 are independently , H or a C 1-6 alkyl group, q1 represents an integer of 0 or more and 10 or less, q2 represents an integer of 1 or more and 10 or less, q3 represents an integer of 1 or more and 10 or less, q1 or When q2 is an integer of 2 or more, a plurality of R 5 or R 6 may be the same or different from each other), R 3 and R 4 are independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, a C 1-20 aliphatic hydrocarbon group, a C 1-20 alkoxyl group, a C 3- 20 cycloalkyl group, C 6-20 aromatic hydro
  • R 9 and R 10 independently represent H or a C 1-6 alkyl group, and when r1 is an integer of 2 or more, multiple R 9 or R 10 may be the same or different from each other.
  • R 11 to R 18 are independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, a C 1-20 aliphatic hydrocarbon group which may have a substituent ⁇ , a substituted Represents a C 1-20 alkoxyl group that may have a group ⁇ or a C 6-12 aromatic hydrocarbon group that may have a substituent ⁇ , R 19 represents a C 1-9 alkylene group which may have a substituent ⁇ , r1 represents an integer of 1 or more and 20 or less, r2 represents an integer of 1 or more and 500 or less. )
  • the substituent ⁇ is one or more halogeno groups selected from the group consisting of a C 1-6 alkoxyl group, a C 1-7 acyl group, chloro, bromo, and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group.
  • one or more substituents selected from The substituent ⁇ is one or more halogeno groups, amino groups, and nitro groups selected from the group consisting of C 1-6 alkyl groups, C 1-6 alkoxyl groups, C 1-7 acyl groups, chloro, bromo, and iodo. , a cyano group, and a carbamoyl group.
  • -(CR 5 R 6 ) q1 - includes, for example, ethylene group (-CH 2 CH 2 -), and -O-(CR 5 R 6 ) q2 - includes, for example, -O-CH 2 CH 2 -- and --O--CH(CH 3 )CH 2 -- may be mentioned.
  • R 1 is -(-O-(CR 5 R 6 ) q2 -) q3 -
  • HO-R 1 -Ph is HO-(-O-(CR 5 R 6 ) q2 -) q3 -Ph, but HO-(-(CR 5 R 6 ) q2 -O-) q3 -Ph.
  • q2 is preferably 2 or more.
  • Examples of the "halogeno group” include chloro, bromo and iodo, with chloro or bromo being preferred, and chloro being more preferred.
  • C 1-20 aliphatic hydrocarbon group refers to a linear or branched monovalent aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, such as a C 1-20 alkyl group, a C 2- Mention may be made of 20 alkenyl groups and C2-20 alkynyl groups. Examples of the C 1-20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl.
  • n-pentadecyl Preferably it is a C 1-10 alkyl group or a C 1-6 alkyl group, more preferably a C 1-4 alkyl group or a C 1-2 alkyl group, even more preferably methyl.
  • Examples of the C 2-20 alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl, pentadecenyl, Examples include icosenyl.
  • it is a C 2-10 alkenyl group or a C 2-6 alkenyl group, more preferably ethenyl (vinyl) or 2-propenyl (allyl).
  • Examples of the C 2-20 alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, icosynyl, and the like.
  • it is a C 2-10 alkynyl group or a C 2-6 alkynyl group, more preferably a C 2-4 alkynyl group or a C 2-3 alkynyl group.
  • C 1-20 alkoxyl group refers to a linear or branched monovalent aliphatic hydrocarbon oxy group having 1 or more and 20 or less carbon atoms.
  • methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy, etc. preferably a C 1-10 alkoxyl group or a C 1-6 alkoxyl group. and more preferably a C 1-4 alkoxyl group or a C 1-2 alkoxyl group, even more preferably methoxy.
  • C 3-20 cycloalkyl group refers to a monovalent cyclic saturated aliphatic hydrocarbon group having 3 or more and 20 or less carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Preferably it is a C 3-10 cycloalkyl group.
  • C 6-20 aromatic hydrocarbon group refers to a monovalent aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms.
  • a "C 7-20 aralkyl group” is an alkyl group substituted with one aromatic hydrocarbon group, and has 7 or more and 20 or less carbon atoms. Examples include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and biphenylmethyl, with benzyl being preferred.
  • C 6-20 aromatic hydrocarbon oxy group refers to a monovalent aromatic hydrocarbon oxy group having 6 or more and 20 or less carbon atoms.
  • phenoxy, indenyloxy, naphthyloxy, biphenyloxy, acenaphthenyloxy, fluorenyloxy, phenalenyloxy, phenanthrenyloxy, anthracenyloxy, anthracenyloxy, triphenylenyloxy examples include pyrenyloxy, chrysenyloxy, naphthacenyloxy, perylenyloxy, etc., preferably a C 6-12 aromatic hydrocarbon oxy group, and more preferably phenoxy.
  • C 3-20 cycloalkoxyl group refers to a monovalent cyclic saturated aliphatic hydrocarbon oxy group having 3 or more and 20 or less carbon atoms.
  • it is a C 3-12 cycloalkyloxy group.
  • substituent ⁇ one or more halogeno groups selected from the group consisting of a C 1-6 alkoxyl group, a C 1-7 acyl group, chloro, bromo, and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group.
  • substituents selected from the groups may be mentioned.
  • substituent ⁇ one or more halogeno groups selected from the group consisting of C 1-6 alkyl group, C 1-6 alkoxyl group, C 1-7 acyl group, chloro, bromo and iodo, amino group, nitro cyano group, and carbamoyl group.
  • Amino group includes an unsubstituted amino group (-NH 2 ), a mono C 1-6 alkylamino group substituted with one C 1-6 alkyl group, and two C 1-6 alkyl groups.
  • the group shall include a substituted di-C 1-6 alkylamino group.
  • Such amino groups include amino (-NH 2 ); methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, t-butylamino, n-pentylamino, n-hexylamino, etc.
  • Mono C 1-6 alkylamino group dimethylamino, diethylamino, di(n-propyl)amino, diisopropylamino, di(n-butyl)amino, diisobutylamino, di(n-pentyl)amino, di(n-hexyl) ) amino, ethylmethylamino, methyl(n-propyl)amino, n-butylmethylamino, ethyl(n-propyl)amino, n-butylethylamino and other diC 1-6 alkylamino groups.
  • it is an unsubstituted amino group.
  • C 1-7 acyl group refers to the atomic group remaining after removing OH from an aliphatic carboxylic acid having 1 or more and 7 or less carbon atoms. Examples include formyl, acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, t-butylcarbonyl, n-pentylcarbonyl, n-hexylcarbonyl, and preferably C 1-4 acyl. group, more preferably acetyl.
  • the number of substituents for the substituent ⁇ is not particularly limited as long as it is substitutable, and may be, for example, 1 or more and 20 or less.
  • the number of substituents is preferably 10 or less, more preferably 5 or less or 3 or less, even more preferably 2 or less or 1.
  • the number of substituents ⁇ is not particularly limited as long as it is substitutable, and may be, for example, 1 or more and 10 or less.
  • the number of substituents is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less or 1.
  • the C 5-20 carbon ring formed by combining R 7 and R 8 includes a C 3-20 cycloalkyl group which may have a substituent ⁇ , and a combination of a cycloalkyl group and an aromatic hydrocarbon group. Mention may be made of fused rings. Examples of the condensed ring include acenaphthenyl and fluorenyl.
  • Examples of the 5-12-membered heterocycle formed by combining R 7 and R 8 include oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, oxathiolanyl, piperidinyl, 1(3H)-isobenzofuranonyl, etc. can be mentioned.
  • diol compound (I 1 ) examples include the following compounds.
  • bis(4-hydroxyphenyl)methane bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, 2,2-bis(4-hydroxyphenyl) ) propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene , 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 1,1-bis(4-hydroxyphenyl)cyclododecane and 1,1-bis(4-hydroxy-3-methyl) Phenyl)cyclododecane is preferred.
  • diol compounds (I 1 ) are shown below. [In the formula, R 1 and R 2 have the same meanings as above. ] However, depending on the case, bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, and bisphenol Z may be excluded from the diol compound (I 1 ).
  • the diol compound (I 2 ) is represented by the following formula (I 2 ). [In the formula, R 1 and R 2 have the same meaning as above, and X 2 has the same meaning as X 1 . ] Specifically, the diol compound (I 2 ) includes 9,9-bis[6-(1-hydroxymethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy) naphthalen-2-yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphthalen-2-yl]fluorene, and 9,9-bis[6-(4-hydroxybutoxy)naphthalen-2-yl ] Fluorene and the like. Among them, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene is preferred.
  • the diol compound (I 3 ) is represented by the following formula (I 3 ).
  • HO-R 1 -X 3 -R 2 -OH (I 3 ) [In the formula, R 1 and R 2 have the same meanings as above, and X 3 represents a C 15-32 divalent aromatic hydrocarbon group.
  • Examples of the C 15-32 divalent aromatic hydrocarbon group include fluoranthenylene, acephenanthrylenylene, aceantrylenylene, triphenylene, pyrenylene, chrysenylene, naphthacenylene, preadenylene, picenylene, peryleneylene, biphenylene, pentaphenylene, C 15-32 divalent fused polycyclic aromatic hydrocarbon groups such as pentathenylene, tetraphenylene, hexaphenylene, hexasenylene, rubisenylene, coronenylene, trinaphthyleneylene, heptaphenylene, heptasenylene, pyrantrenylene, ovalenylene; terphenylene and Examples include quarter phenylene.
  • the number of R 3 groups on X 3 is not particularly limited as long as it can be substituted, but can be, for example, 1 or more and 10 or less, preferably 8 or
  • diol compound (I 3 ) examples include binaphthalene diol compounds represented by the following formula. [In the formula, R 1 and R 2 have the same meanings as above. ]
  • binaphthalenediol compounds include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, Examples include 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthalene and 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is preferred.
  • the diol compound (I 4 ) is represented by the following formula (I 4 ). However, isosorbide which induces the structural units (A) and (B) is excluded from the diol compound (I 4 ).
  • HO-R 20 -X 4 -R 21 -OH (I 4 ) [In the formula, R 20 and R 21 are independently -(CR 5 R 6 ) m1 - or -(-O-(CR 5 R 6 ) m2 -) m3 - (wherein R 5 and R 6 have the same meanings as above) m 1 represents an integer of 1 or more and 10 or less, m 2 represents an integer of 1 or more and 10 or less, m 3 represents an integer of 1 or more and 10 or less, and m 1 or m 2 represents an integer of 1 or more and 10 or less. When it is an integer, a plurality of R 5 or R 6 may be the same or different from each other), X 4 represents a divalent group containing one or more hydrocarbon rings or heterocycle
  • -(CR 5 R 6 ) m1 - includes, for example, ethylene group (-CH 2 CH 2 -), and -O-(CR 5 R 6 ) m2 - includes, for example, -O-CH 2 CH 2 -- and --O--CH(CH 3 )CH 2 -- may be mentioned.
  • R 1 is -(-O-(CR 5 R 6 ) m2 -) m3 -
  • HO-R 1 -X 3 - is HO-(-O-(CR 5 R 6 ) m2 -) m3 -X 3 -, but HO-(-(CR 5 R 6 ) m2 -O-) m3 -X 3 -.
  • the divalent group containing one or more hydrocarbon rings or heterocycles includes a divalent C 6-32 aromatic hydrocarbon group which may have a substituent ⁇ , a divalent group which may have a substituent ⁇ , 1 C 3-20 cycloalkyl group, a divalent C 6-32 aromatic hydrocarbon group which may have a substituent ⁇ , and a divalent C 3-20 cycloalkyl group which may have a substituent ⁇ , respectively.
  • Divalent groups having the above can be mentioned.
  • the divalent C 6-32 aromatic hydrocarbon group may contain a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom, as long as it exhibits aromaticity as a whole.
  • the divalent C 6-32 aromatic hydrocarbon group is not particularly limited, but the following can be mentioned.
  • the divalent C 3-20 cycloalkyl group may also contain a heteroatom selected from oxygen, sulfur, and nitrogen atoms.
  • the divalent C 3-14 cycloalkyl group is not particularly limited, but the following can be mentioned.
  • the diol compound (I 5 ) is represented by the following formula (I 5 ). HO-R 1 -X 5 -R 2 -OH (I 5 ) [In the formula, R 1 and R 2 represent the same meanings as above, and X 5 represents a divalent saturated heterocyclic group. ]
  • the divalent saturated heterocyclic group is not particularly limited, but the following can be mentioned.
  • the diol compound (I 6 ) is represented by the following formula (I 6 ).
  • X 6 represents a C 1-10 alkylene group
  • n represents an integer of 13 or more and 50 or less.
  • the C 1-10 alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms.
  • -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH(CH 3 )CH 2 -, -CH 2 CH 2 CH 2 CH 2 - may be mentioned.
  • X 6 in the diol compound (I 6 ) may be the same or different from each other, and when multiple X 5 exist, the arrangement of -O-X 6 - may be random or block-like. It may be.
  • the C 1-10 alkylene group is preferably a C 2-10 alkylene group.
  • One type of diol compound may be used alone, or two or more types may be used in combination. For example, by using two or more types of diol compounds in combination, a copolymerized polycarbonate can be produced satisfactorily. However, from the viewpoint of manufacturing efficiency and the like, it is preferable to use only one type of diol compound alone.
  • the number of diol compounds is preferably 5 or less, more preferably 3 or less, and even more preferably 2.
  • the amount of the C 1-4 halogenated hydrocarbon and diol compound to be used is not particularly limited as long as the reaction proceeds and the desired product is obtained.
  • the above reaction also proceeds when using 1 times the molar amount of the diol compound.
  • the molar ratio of the diol compound to the C 1-4 halogenated hydrocarbon should be set to 0.001 or more. The following is preferable.
  • the molar ratio is more preferably 0.01 or more, even more preferably 0.1 or more, more preferably 0.8 or less, and even more preferably 0.5 or less.
  • the ratio of the diol compound to the C 1-4 halogenated hydrocarbon should be 1 mg/mL or more and 500 mg/mL or more. /mL or less.
  • Thermoplastic resins include random copolymers and block copolymers consisting only of structural units (A) and (B), structural units (A) and structural units (B), and other structural units, such as structural units. It may be either a random copolymer or a block copolymer containing the unit (Z). From the viewpoint of properties, simplification of manufacturing process, etc., the thermoplastic resin is preferably a random copolymer. Further, it is preferable that the number of mutually bonded structural units (A) and mutually bonded structural units (B) is small, and the structural units (A) and structural units (B) are bonded alternately as much as possible. .
  • the total content of structural units other than the structural unit (A) and the structural unit (B), such as the structural unit (Z), in the thermoplastic resin that is, the composition in terms of the number of moles of all the structural units of the thermoplastic resin.
  • the ratio of the total number of moles of structural units other than the unit (A) and the structural unit (B) is, for example, 50 mol% or less or less.
  • the ratio of the total number of moles of structural units other than the structural unit (A) and the structural unit (B) in the thermoplastic resin is preferably less than or equal to 40 mol%, more preferably less than or equal to 30 mol%. Preferably, it is 20 mol% or less, 15 mol% or less, or more preferably 10 mol% or less.
  • the content of the structural unit (Z) in the thermoplastic resin is, for example, 50 mol% or less or less, preferably 40 mol% or less or less, more preferably 30 mol% or less, and 20 mol% or less. More preferably, it is less than or equal to mol %, less than or equal to 15 mol %, or less than or equal to 10 mol %.
  • the weight average molecular weight of the thermoplastic resin is, for example, 10,000 to 300,000, preferably 10,000 to 200,000, and more preferably 10,000 to 100,000.
  • the weight average molecular weight of the thermoplastic resin is more preferably 15,000 to 60,000, more preferably 18,000 to 50,000, particularly preferably 20,000 to 45,000.
  • the number average molecular weight of the thermoplastic resin is, for example, 3,000 to 100,000, preferably 3,000 to 70,000, and more preferably 5,000 to 50,000.
  • the number average molecular weight of the thermoplastic resin is more preferably 7,000 to 40,000, more preferably 8,000 to 35,000, particularly preferably 10,000 to 30,000.
  • the Q value (melt flow volume per unit time (10 -2 ml/sec) measured at 240°C and a load of 160 kg) is 3 to 120 (10 -2 ml/sec).
  • the Q value is more preferably 3 to 60 (10 ⁇ 2 ml/sec), still more preferably 4 to 40 (10 ⁇ 2 ml/sec), and particularly preferably 5 to 32 (10 ⁇ 2 ml/sec). 2 ml/sec)).
  • the lower limit of the melt flow volume is, for example, 2.0 (10 -2 ml/sec) or more, 2.5 (10 -2 ml/sec) or more, 3 .0 (10 -2 ml/sec) or more, 3.5 (10 -2 ml/sec) or more, 4.0 (10 -2 ml/sec) or more, 4.5 (10 -2 ml/sec) or more , 5.5 (10 ⁇ 2 ml/sec) or more.
  • the upper limit of the Q value is, for example, 180 (10 -2 ml/sec) or less, 150 (10 -2 ml/sec) or less, 120 (10 -2 ml/sec) or less, 60 (10 -2 ml/sec) or less, 40 (10 -2 ml/sec) or less sec) or less, or 32 (10 -2 ml/sec) or less, but 25 (10 -2 ml/sec) or less, 20 (10 -2 ml/sec) or less, 15 (10 -2 ml/sec) below, it may be 10 (10 -2 ml/sec) or less, etc.
  • the glass transition temperature (Tg) according to JIS K 7121 is, for example, 50 to 160°C.
  • the Tg range of the thermoplastic resin is preferably 80 to 160°C, more preferably 85 to 150°C, and even more preferably 100 to 145°C.
  • the YI value measured according to JIS K 7373 is 15.0 or less.
  • the YI value range of the thermoplastic resin is more preferably 12.0 or less, even more preferably 10.0 or less, and particularly preferably 8.0 or less.
  • the ratio of the total weight of silicon atoms (total Si amount) based on the total weight of the thermoplastic resin is, for example, 0.4 to 10.0% by mass, and 1.0 to 10.0% by mass. It is preferably % by mass, more preferably 1.2-8.0% by mass, even more preferably 1.5-7.0% by mass, 2.0-6.5% by mass, For example, it is particularly preferably 2.0 to 4.0% by mass.
  • the proportion of carbonate-derived Ph terminal groups is preferably 0.1 to 20 ⁇ eq/g, and 0.5 to 18 ⁇ eq. /g, more preferably 1.0 to 16 ⁇ eq/g, particularly preferably 1.5 to 12 ⁇ eq/g.
  • the proportion of carbonate-derived Ph terminal groups is preferably 1 to 20 mol%, more preferably 2 to 18 mol%, and 3 to 20 mol%, based on the total number of terminal groups in the polymer chain of the thermoplastic resin. It is more preferably 15 mol%, and particularly preferably 4 to 12 mol%.
  • the proportion of Ph end groups derived from silyl ether is 5 to 200 ⁇ eq/g. It is preferably 10 to 150 ⁇ eq/g, even more preferably 15 to 120 ⁇ eq/g, and particularly preferably 20 to 100 ⁇ eq/g.
  • the proportion of Ph terminal groups derived from silyl ether is preferably 30 to 99 mol%, more preferably 40 to 95 mol%, based on the total number of terminal groups in the polymer chain of the thermoplastic resin, and more preferably 40 to 95 mol%.
  • the isosorbide-derived double bond end group (for example, has the structure -OC(O)-O-ISB, and the hydroxyl group is removed from the 5-membered ring of the isosorbide group represented by ISB).
  • the proportion of terminal groups (terminal groups, etc. with double bonds formed therein, from which the hydroxyl group has been removed and an isosorbide ring containing a double bond is placed at the end) is 60 ⁇ eq/g or less. is preferable, and preferably as low as possible.
  • Preferred ranges of the ratio of isosorbide-derived double bond terminal groups are, for example, 0.1 to 60 ⁇ eq/g, 0.1 to 30 ⁇ eq/g, 0.1 to 15 ⁇ eq/g, 0.1 to 12 ⁇ eq/g, etc. .
  • the proportion of isosorbide-derived double bond terminal groups is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, based on the number of total terminal groups in the polymer chain of the thermoplastic resin. More preferably, it is 3 to 30 mol%.
  • the thermoplastic resin polymer may contain some impurities.
  • the content of impurities such as those derived from raw materials such as formic acid and organic phosphorus compounds is 5 ppm or more and 100 ppm by weight or less, and 10 ppm or more and 70 ppm or more, based on the total weight of the polymer. It may be contained in an amount of not more than 20 ppm by weight and not more than 50 ppm by weight. Further, in the thermoplastic resin, some amount of the catalyst used in the polymerization reaction for production may remain.
  • the metal equivalent amount is, for example, 5 ⁇ mol or more and 100 ⁇ mol or less, 15 mole or more and 80 ⁇ mol or less, 25 mole or more and 60 ⁇ mol or less, and 30 ⁇ mol.
  • the residual catalyst may be contained in an amount of 50 ⁇ mol or less.
  • the method for producing a thermoplastic resin in the present invention includes a step of polymerizing monomer compounds (i) to (iii), that is, (i) an isosorbide compound represented by the above general formula (3), including isosorbide and/or its Both stereoisomers include a step of polymerizing (ii) a carbonate compound and (iii) a silane compound, both of which will be described in detail later.
  • the carbonate compound functions as a source of carbonate bonding sites in the structural unit (A)
  • the silane compound functions as a source of carbonate bonding sites in the structural unit (B) (“-O-Si-O-”). act as a source of binding sites).
  • thermoplastic resin is obtained. That is, it is a thermoplastic resin having a carbonate structural unit (A) produced, for example, by the reaction of the following formula (a), and a silyl ether constituent unit (B) produced, for example, by the reaction of the following formula (b). .
  • aryl alcohol such as phenol (PhOH) is produced as a by-product. Therefore, in the polymerization step, it is preferable to proceed with the polymerization reaction under reduced pressure while removing the by-product alcohol, for example, an aryl alcohol such as phenol, while the mixture of the above-mentioned components is melted.
  • thermoplastic resin according to the present invention
  • Isosorbide compound> In the polymerization reactions represented by formulas (a) and (b) above, the isosorbide compound of formula (3), ie, isosorbide, isomannide and/or isoidet, is used. That is, in the polymerization reactions of formulas (a) and (b), isosorbide (1,4:3,6-dianhydro-D-sorbitol), isomannide, or isoidet can be used. As described above, according to the method for producing a thermoplastic resin of the present invention, a copolymer having different structural units can be efficiently produced from a relatively small number of types of raw materials.
  • the carbonate compound is used to introduce a carbonyl group (-CO- group) of a polycarbonate structural unit into a thermoplastic resin, as shown in the above formula (a) regarding the outline of the polymerization reaction. That is, two -OR groups of a carbonate compound represented by the general formula RO-CO-OR (R is each independently selected from an aryl group, an alkyl group, and an aralkyl group), for example, a carbonate compound is generally The two aryloxy groups (ArO- groups) in the diaryl carbonate represented by the formula ArO-CO-OAr are not introduced into the polymer chain of the thermoplastic resin. These -OR groups produce alcohol derived from a carbonate compound as a by-product. For example, a carbonate compound (monoaryl carbonate or diaryl carbonate) having an aryloxy group (ArO- group) is Produces aryl alcohol (ArOH), a by-product such as phenol.
  • aryl alcohol ArOH
  • the types of aryl groups, alkyl groups, and aralkyl groups of the carbonate compound are not particularly limited.
  • the -OR group in the above general formula is replaced with an aryloxy group (or the -R group in the above general formula RO-CO-OR is replaced with an aryloxy group).
  • the carbonate compound preferably has low polarity and low molecular weight, and the -OR group in the above general formula is, for example, a phenoxy group.
  • either or both of the above Ar groups is preferably an aryl group having a total carbon number of 10 or less, such as a phenyl group or a benzyl group.
  • preferred specific examples of carbonate compounds include diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate, but dimethyl carbonate, diethyl carbonate, and dibutyl carbonate are preferred.
  • dialkyl carbonates such as dicyclohexyl carbonate, or monoaryl monoalkyl carbonates.
  • the above-mentioned carbonate compound can be synthesized by a known method, or a commercially available one may be used.
  • Silane compound used in the polymerization step is used to form a structural unit (B) containing a silyl ether bonding site in a thermoplastic resin, for example as shown in the above formula (b).
  • the type of silane compound is not particularly limited as long as it is possible to form a siloxane structural unit containing an -OSi(R 1 R 2 ) O- site in the main chain of the thermoplastic resin, details of which will be described later. It is selected from diaryloxysilane compounds, certain dialkoxysilane compounds, and certain silicon compounds (siloxane compounds).
  • a silane compound containing at least one of a diaryloxysilane compound, a dialkoxysilane compound, and a silicon compound is used.
  • a silane compound a plurality of diaryloxysilane compounds may be used in combination, a plurality of dialkoxysilane compounds may be used in combination, a plurality of silicon compounds may be used in combination, and a diaryloxysilane compound and a silicon compound may be used in combination.
  • a mixture of a dialkoxysilane compound and a silicon compound, a mixture of a diaryloxysilane compound and a dialkoxysilane compound may be used.
  • the diaryloxysilane compound will be explained below.
  • diaryloxysilane compound examples include dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane. That is, in the polymerization step, any one or more of these may be used as the silane compound.
  • a diaryloxysilane compound is represented by the general formula Si(Rs 1 Rs 2 )(OAr) 2
  • Rs 1 and Rs 2 are each independently selected from an alkyl group and an aryl group. It is preferable that Rs 1 and Rs 2 are each independently an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, and an aryl group having a total of 6 to 30 carbon atoms. More preferably, when Rs 1 and Rs 2 are an alkyl group that may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6. Preferably, the total number of carbon atoms is 1 or 2, particularly preferably. Further, when Rs 1 and Rs 2 are an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, It is particularly preferred that the total number of carbon atoms is 6 to 8.
  • substituents examples include hydroxyl group, halogen, amino group, vinyl group, carboxyl group, cyano group, (meth)acryloxy group, glycidyloxy group, and mercapto group.
  • Preferred specific examples of Rs 1 and Rs 2 include a methyl group, a phenyl group, a vinyl group, and a propyl group, with a methyl group being more preferred.
  • the aryloxy group (OAr group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but is introduced into by-products such as phenol ( ArOH) is generated. Therefore, the type of aryloxy group is not particularly limited. However, the aryloxy group preferably has low polarity and low molecular weight, such as a phenoxy group, so that by-products in the polymerization process can be removed from the reaction system as easily as possible.
  • dialkyldiaryloxysilane examples include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane, etc.
  • diaryldiaryloxysilane examples include diphenyldiphenoxysilane.
  • specific examples of the monoalkylmonoaryldiaryloxysilane include methylphenylphenoxysilane and the like.
  • dialkoxysilane compound examples include dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane. That is, in the polymerization step, any one or more of these may be used as the silane compound.
  • a dialkoxysilane compound is represented by the general formula Si(Rs 1 Rs 2 )(OR C ) 2
  • Rs 1 Rs 2 are each independently Rs described in the column of (A-1) diaryloxysilane compound. 1 Rs Same as 2 , selected from alkyl groups and aryl groups.
  • the alkoxy group (OR C group) of the silane compound is not introduced into the polymer chain of the thermoplastic resin, but is introduced into by-products such as methanol (MeOH). ). Therefore, the type of alkoxy group is not particularly limited.
  • the alkoxy group ( ORC group) is, for example, a methoxy group so that by-products in the polymerization process can be removed from the reaction system as easily as possible.
  • dialkyldialkoxysilane examples include dimethyldimethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, etc.
  • diaryldialkoxysilane examples include diphenyldimethoxysilane.
  • monoalkylmonoaryldialkoxysilane examples include methylphenyldimethoxysilane and the like.
  • Silicon compounds (siloxane compounds)
  • the silicon compound will be explained below.
  • Examples of the silicon compound include certain cyclic siloxane compounds and linear siloxane compounds. That is, in the polymerization step, any of these may be used as the silane compound.
  • the siloxane compound used in the polymerization process includes a cyclic siloxane compound represented by the following formula (5).
  • R c and R d each independently represent an alkyl group, an alkenyl group, or an aryl group that may have a substituent.
  • R c and R d in formula (5) are each preferably an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms.
  • R c and R d are an alkyl group that may have a substituent
  • the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and the total number of carbon atoms is preferably 1 to 10. It is particularly preferred that the number is 1 or 2.
  • R c and R d are an aryl group which may have a substituent
  • the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, It is particularly preferred that the total number of carbon atoms is 6 to 8.
  • substituents examples include hydroxyl group, halogen, amino group, vinyl group, carboxyl group, cyano group, (meth)acryloxy group, glycidyloxy group, and mercapto group.
  • Preferred specific examples of R c and R d in formula (5) include a methyl group, a phenyl group, a vinyl group, and a propyl group.
  • the cyclic siloxane compound has a siloxane structure, and examples of the siloxane structure include the -OSi(R c R d )O- structure having the above-mentioned R c group and R d group.
  • the -OSi(R c R d )O- moiety of such a cyclic siloxane compound is introduced into the thermoplastic resin, the details of which will be described later.
  • n represents an integer from 3 to 30.
  • the value of n in formula (5) is preferably 3 or more and 15 or less, more preferably 3 or more and 10 or less, still more preferably 3 or more and 8 or less, particularly preferably 3 or more and 5 or less. It is.
  • the molecular weight of the cyclic siloxane compound represented by formula (5) is preferably 2,000 or less, more preferably 1,600 or less, even more preferably 1,200 or less, and 1,000 or less. The following is particularly preferred. Further, the molecular weight of the cyclic siloxane compound represented by formula (5) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.
  • the siloxane compound used in the polymerization process also includes a linear siloxane compound represented by the following formula (6).
  • R e and R f each independently represent an alkyl group or an aryl group that may have a substituent.
  • R e and R f in formula (6) are each preferably an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms.
  • the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and the total number of carbon atoms is preferably 1 to 10.
  • the number is 1 or 2.
  • R e and R f are an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, It is particularly preferred that the total number of carbon atoms is 6 to 8.
  • substituents examples include hydroxyl group, halogen, amino group, vinyl group, carboxyl group, cyano group, (meth)acryloxy group, glycidyloxy group, and mercapto group.
  • Preferred specific examples of R e and R f in formula (6) include a methyl group, a phenyl group, a vinyl group, and a propyl group.
  • the linear siloxane compound also has a siloxane structure, and examples of the siloxane structure include the -OSi(R e R f )O- structure having the above-mentioned R e group and R f group.
  • the -OSi(R e R f )O- moiety of the linear siloxane compound is introduced into the thermoplastic resin, the details of which will be described later.
  • m represents an integer from 2 to 10,000.
  • the value of m in formula (6) is preferably 10 or more and 7,000 or less, more preferably 100 or more and 2,000 or less, and even more preferably 200 or more and 500 or less.
  • X is each independently a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have a substituent, an oxygen atom or a nitrogen atom, which may have a substituent. represents a hydrocarbon group having a total of 1 to 10 carbon atoms which may have a substituent, or an amino group which may have a substituent.
  • each X independently has a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms in total that may have a substituent, an oxygen atom, or a nitrogen atom, which may have a substituent.
  • An alkyl group having a total of 1 to 10 carbon atoms which may have a substituent more preferably a hydroxyl group or an alkyl group having a total of 1 to 10 carbon atoms which may have a substituent. , a hydroxyl group, or an alkyl group having a total of 1 to 5 carbon atoms.
  • substituent for X mentioned above include a hydroxyl group, halogen, amino group, vinyl group, carboxyl group, cyano group, (meth)acryloxy group, glycidyloxy group, and mercapto group.
  • the molecular weight of the linear siloxane compound represented by formula (6) is preferably 60,000 or less, more preferably 56,000 or less, even more preferably 50,000 or less, 45, 000 or less is particularly preferable. Further, the molecular weight of the linear siloxane compound represented by formula (6) is, for example, 1,000 or more, preferably 5,000 or more, and more preferably 10,000 or more.
  • cyclic siloxane compound of the above formula (5) and the linear siloxane compound represented by the following formula (6) only a single siloxane compound may be used, or two or more types of siloxane compounds may be used. It may also be used as a mixture. Further, the siloxane compound of formula (5) or formula (6) may be used in combination with the above-mentioned (A) diaryloxysilane compound. Note that the above-mentioned silane compound can be synthesized by a known method, or a commercially available one may be used.
  • any monomer> In addition to the above-mentioned monomer compounds, that is, (i) isosorbide compounds, (ii) carbonate compounds, and (iii) silane compounds, monomers for forming arbitrary structural units may be used in the polymerization reaction.
  • monomers for forming the arbitrary structural unit include diol compounds for forming the above-mentioned arbitrary structural unit (Z).
  • the total mole ratio with the silane compound is, for example, 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, 80 mol% or more, or 90 mol% or more. It is more preferable that Furthermore, in the method for producing a thermoplastic resin, it is particularly preferable to substantially or completely use only (i) an isosorbide compound, (ii) a carbonate compound, and (iii) a silane compound as monomers.
  • the molar ratio of (ii) carbonate compound and (iii) silane compound is preferably 40/60 to 95/5, more preferably 50/50 to 90/10 or 60/40 to 92/8. Yes, more preferably 70/30 to 90/10.
  • the molar ratio of the amount of (i) isosorbide compound used in the polymerization step for producing the thermoplastic resin to the total amount of (ii) carbonate compound and (iii) silane compound is 25/75 to 60/40.
  • the ratio is preferably 30/70 to 55/45, and even more preferably 35/65 to 47/53.
  • the molar amount of (i) the isosorbide compound is preferably slightly smaller than the total amount of (ii) the molar amount of the carbonate compound and (iii) the molar amount of the silane compound.
  • the ratio of the molar amount of (i) the isosorbide compound to the molar amount of (ii) the carbonate compound in the polymerization step is preferably 40/60 to 80/20, for example, 50/50 to 65/35. . Further, the ratio of the molar amount of (i) the isosorbide compound to the molar amount of (iii) the silane compound in the polymerization step is preferably from 60/40 to 90/10, for example from 70/30 to 87/13. It is.
  • Antioxidants are used in polymerization reactions for producing thermoplastic resins.
  • the order of mixing does not matter, it is recommended that not only monomer compounds (i) to (iii) but also an antioxidant be mixed in advance with monomer compounds (i) to (iii) before starting the polymerization reaction.
  • monomer compounds (i) to (iii) are preferably polymerized in the presence of a transesterification catalyst described below.
  • antioxidants include phosphite additives, phenolic antioxidants, hindered phenolic antioxidants, bisphenol antioxidants, polyphenol antioxidants, sulfur antioxidants, etc.
  • phosphite additives are used.
  • Specific examples of the phosphite-based antioxidant include organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like.
  • phosphorous acid ester compounds (a), phosphorous acid (b) and tetrakis ester compounds in which at least one ester in the molecule is esterified with phenol and/or a phenol having at least one alkyl group having 1 to 25 carbon atoms; At least one selected from the group of (2,4-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite (c) can be mentioned.
  • phosphite compound (a) examples include trioctyl phosphite, triotadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, and tris(monononylphenyl) phosphite.
  • organic phosphite compounds for example, "Adeka Stab 1178 (product name, same hereinafter)", “Adeka Stab 2112", “Adeka Stab HP-10” manufactured by Adeka Corporation, “JP-351”, “JP-360” manufactured by Johoku Kagaku Kogyo Co., Ltd. ", “JP-3CP”, “Irgafoss 168” manufactured by BASF, etc.
  • Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and the like.
  • phenolic antioxidants 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, n-octadecyl-3-(3 ',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'- Butylidene bis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis ⁇ 2-[ 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro[5,5]und
  • phenolic antioxidants examples include “Irganox 1010” (registered trademark, same hereinafter) manufactured by BASF, “Irganox 1076", “Adeka Stab AO-50", “Adeka Stab AO-60” manufactured by Adeka, etc. be able to.
  • the addition ratio of the antioxidant is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, based on 100 parts by mass, which is the total of the monomer compounds of the thermoplastic resin. More preferably, the amount is 0.05 part by mass or more, and preferably 1 part by mass or less, more preferably 0.5 part by mass or less, still more preferably 0.3 part by mass or less, or 0.1 part by mass or less.
  • the content of phosphorus in the thermoplastic resin due to phosphite-based antioxidants is also, for example, 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.1 part by mass. Parts by mass or less.
  • the antioxidant may contain only one type, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • thermoplastic resin composition containing an antioxidant by adding an antioxidant to a thermoplastic resin produced by a polymerization reaction.
  • additives have been added after resin production in order to prevent thermal history of the additives themselves that occur during polymerization reactions, or to enable adjustment of the amount added depending on the purpose of use. many.
  • the method for producing a thermoplastic resin of the present invention in which an antioxidant is added to the monomer compound before the polymerization reaction, the effect of improving the hue of the produced thermoplastic resin was remarkable.
  • the transesterification catalyst used in the polymerization step is preferably a catalyst containing a basic compound.
  • Basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Such compounds include organic acid salts, carbonates, etc. of alkali metals and alkaline earth metal compounds, etc. Examples include inorganic salts, oxides, hydroxides, hydrides, and alkoxides of. Alternatively, quaternary ammonium hydroxide, salts thereof, amines, etc. are used as the basic compound catalyst. Moreover, these compounds can be used alone or in combination of multiple types.
  • the transesterification catalyst more preferably contains an alkali metal carbonate or an alkali metal hydroxide.
  • specific examples of more preferred transesterification catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, and the like.
  • a phosphonium salt or the like can be used, and a quaternary phosphonium salt is preferable.
  • phosphonium salt as a polymerization catalyst examples include tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, and tetraphenylphosphonium phenoxide.
  • transesterification catalysts include the following.
  • alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, and carbonate.
  • alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, and the like.
  • basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, and tributyl.
  • Examples include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, strontium salts, etc.
  • Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salts, and the like.
  • Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, Examples include butyltriphenylammonium hydroxide.
  • Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2- Examples include dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.
  • transesterification catalyst can be prepared by a known method, and a commercially available one may also be used. Further, in thermoplastic resins and thermoplastic resin compositions whose details will be described later, it is preferable to substantially completely remove transesterification catalysts, such as alkali metal compound catalysts and alkaline earth metal compound catalysts. .
  • the polymerization reaction is preferably allowed to proceed under a pressure of 400 Pa or less. That is, the pressure in the polymerization reaction is preferably within a range of 400 Pa or less.
  • the pressure in the polymerization reaction is preferably within a range of 400 Pa or less.
  • the reaction pressure is increased from the initial atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. It is preferable to gradually reduce the pressure to 400 Pa or less. In this way, the pressure reduction step in which the pressure inside the reaction system is reduced stepwise and the degree of pressure reduction is increased midway through is preferable because it is possible to efficiently remove alcohol as a by-product while suppressing distillation of raw materials.
  • the time for the polymerization step is determined as appropriate, taking into account conditions such as the type of thermoplastic resin to be used, pressure, and temperature; however, for example, the total time for the polymerization step is within 5 to 10 hours. More specifically, the reaction time before reducing the pressure in the reaction system is, for example, 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after reducing the pressure is, for example, 0.5 to 6 hours, preferably. is 0.8 to 4 hours.
  • the temperature in the above polymerization reaction is preferably within the range of 150 to 300°C. More preferably, the temperature of the polymerization reaction is 160 to 260°C, even more preferably 170 to 240°C, particularly preferably 180 to 230°C.
  • the ratio of the molar amount of the transesterification catalyst to the total molar amount of the isosorbide compounds is 1.0 ⁇ 10 -7 to 1.0 ⁇ 10 ⁇ 2 (mol/mol: 0.1 to 10000 ⁇ mol/mol, or 1.0 ⁇ 10 ⁇ 4 to 10 mmol/mol).
  • the above molar ratio is more preferably 1.0 ⁇ 10 ⁇ 7 to 2.0 ⁇ 10 ⁇ 5 mol/mol (or 0.1 to 20 ⁇ mol/mol).
  • the ratio of the total molar amount of the isosorbide compound and the diol compound to the molar amount of the transesterification catalyst is preferably within the above-mentioned range.
  • thermoplastic resin composition preferably contains the above-mentioned polycarbonate-polysilyl ether resin as a main component.
  • the thermoplastic resin composition of the present invention may contain the following components in addition to the polycarbonate-polysilyl ether resin. ⁇ 1.
  • the thermoplastic resin composition may contain a cyclic body represented by the following general formula (K).
  • Rs 1 and Rs 2 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 6 to 30 carbon atoms which may have a substituent. is an aryl group.
  • the total number of carbon atoms is preferably 1 to 10, and the total number of carbon atoms is preferably 1 to 6. More preferably, the total number of carbon atoms is 1 or 2, particularly preferably. Further, when Rs 1 and Rs 2 are an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, It is particularly preferred that the total number of carbon atoms is 6 to 8.
  • Examples of the substituents for Rs 1 and Rs 2 above include, each independently, a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, etc. .
  • Preferred specific examples of Rs 1 and Rs 2 include a methyl group, a phenyl group, a vinyl group, and a propyl group, with a methyl group being more preferred.
  • n 1 to 3, preferably 2 or 3, and more preferably 2.
  • the above-mentioned cyclic bodies contained in the thermoplastic resin composition of the present invention may be produced as by-products in the polymerization reaction for producing polycarbonate-polysilyl ether resins, and have a low molecular weight, so they may be included in the composition. It may have the effect of improving fluidity.
  • the total content of the cyclic bodies represented by the above formula (K) is preferably 4.0% by weight or less, more preferably 4.0% by weight or less based on the total weight of the thermoplastic resin composition. is 3.0% by weight or less, more preferably 2.0% by weight or less, particularly preferably 1.0% by weight or less.
  • thermoplastic resin composition of the present invention does not need to contain the above-mentioned cyclic body.
  • the thermoplastic resin composition of the present invention preferably contains an antioxidant.
  • the antioxidant the above-mentioned phosphite antioxidants are preferred.
  • the thermoplastic resin composition preferably contains an antioxidant used in the polymerization reaction for producing the polycarbonate-polysilyl ether resin.
  • the addition ratio of the antioxidant in the thermoplastic resin composition is preferably 0.001 parts by mass or more (approximately 10 parts by mass or more), more preferably 0.001 parts by mass or more (approximately 10 parts by mass or more), based on 100 parts by mass of the entire composition. 0.1 part by mass or more (approximately 100 mass ppm or more), more preferably 0.1 part by mass or more (approximately 1000 mass ppm or more). Further, the addition ratio of the antioxidant in the thermoplastic resin composition is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, based on 100 parts by mass of the entire composition.
  • the antioxidant may contain only one type, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the thermoplastic resin composition of the present invention may contain the following additives as secondary components.
  • Deactivator After the polymerization reaction is completed, the catalyst may be removed or deactivated from the thermoplastic resin of the present invention in order to maintain thermal stability.
  • a known method of deactivating the catalyst by adding an acidic substance can be suitably carried out.
  • acidic substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
  • Phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-phosphite Phosphite esters such as n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphoric acid Phosphoric acid esters such as dioctyl and monooctyl phosphate; Phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; Phosphonic acid esters such as diethyl
  • alkyl sulfates such as dimethyl sulfate; organic halides such as benzyl chloride, etc. are preferably used.
  • alkyl acid phosphate metal salts such as distearyl acid phosphate zinc salt and monostearyl acid phosphate zinc salt may be used.
  • the above catalyst deactivator may be used, for example, from 0.001 to 50 times, preferably from 0.01 to 30 times, the amount of the catalyst.
  • the above-mentioned catalyst deactivator which is an acidic substance, in an amount of 1.0 equivalent or more (1 times the mole or more) relative to the amount of the polymerization catalyst, for example, about 1.0 to 20 times the mole, May be used.
  • a stabilizer may be added to the thermoplastic resin of the present invention.
  • the stabilizer include thermal stabilizers and the above-mentioned antioxidants.
  • the addition ratio of the stabilizer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.02 parts by mass or more, based on 100 parts by mass of the thermoplastic resin.
  • the content is preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and even more preferably 1.0 parts by mass or less.
  • the stabilizer may contain only one type, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • heat stabilizer examples include phenol-based, phosphorus-based, and sulfur-based heat stabilizers.
  • phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid
  • acidic pyrophosphate metal salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate
  • phosphoric acid examples include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.
  • phosphorous acid ester compounds (a), phosphorous acid (b) and tetrakis ester compounds in which at least one ester in the molecule is esterified with phenol and/or a phenol having at least one alkyl group having 1 to 25 carbon atoms; At least one selected from the group of (2,4-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite (c) can be mentioned.
  • phosphite compound (a) examples include trioctyl phosphite, triotadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, and tris(monononylphenyl) phosphite.
  • organic phosphite compounds for example, "Adeka Stab 1178 (product name, same hereinafter)", “Adeka Stab 2112", “Adeka Stab HP-10” manufactured by Adeka Corporation, “JP-351”, “JP-360” manufactured by Johoku Kagaku Kogyo Co., Ltd. ", “JP-3CP”, “Irgafoss 168” manufactured by BASF, etc.
  • phosphoric acid esters examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and the like.
  • the addition ratio of the heat stabilizer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.03 parts by mass or more, based on 100 parts by mass of the thermoplastic resin.
  • the amount is preferably 1 part by mass or less, more preferably 0.7 part by mass or less, even more preferably 0.5 part by mass or less.
  • the heat stabilizer may contain only one type, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.
  • thermoplastic resin composition of the present invention may contain various additives without departing from the spirit of the present invention.
  • the additive include at least one additive selected from flame retardants, flame retardant aids, ultraviolet absorbers, mold release agents, and colorants, and at least one of the flame retardants and mold release agents. is preferred.
  • antistatic agents, optical brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc. may be added as long as desired physical properties are not significantly impaired.
  • thermoplastic resin of the present invention may contain various additives without departing from the spirit of the present invention.
  • flame retardant organic metal salt flame retardants, phosphorus flame retardants, silicone flame retardants, etc. may be blended.
  • flame retardants that can be used in the present invention include flame retardants (flame retardant compositions) described in paragraphs 0085 to 0093 of JP 2016-183422A, the contents of which are incorporated herein.
  • Ultraviolet absorbers As ultraviolet absorbers, in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, ogizanilide compounds, malonic acid ester compounds, hindered amine compounds, Examples include organic ultraviolet absorbers such as phenyl salicylate compounds. Among these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.
  • benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis( ⁇ , ⁇ -dimethylbenzyl) phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'- methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3- tetramethylbutyl
  • benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy- Benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2',4, Examples include 4'-tetrahydroxy-benzophenone.
  • phenyl salicylate ultraviolet absorber examples include phenyl salicylate, 4-tert-butyl-phenyl salicylate, and the like.
  • triazine-based ultraviolet absorbers examples include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4 , 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol and the like.
  • hindered amine ultraviolet absorber bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the like can be mentioned.
  • the addition ratio of the ultraviolet absorber is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 3 parts by mass, based on 100 parts by mass of the thermoplastic resin.
  • the amount is more preferably 1 part by mass or less.
  • One type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • Mold release agent examples include carboxylic acid esters, polysiloxane compounds, paraffin wax (polyolefin type), and the like. Specifically, at least one compound selected from the group of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils is mentioned. be able to.
  • aliphatic carboxylic acids mention may be made of saturated or unsaturated aliphatic mono-, di- or trivalent carboxylic acids.
  • aliphatic carboxylic acid also includes alicyclic carboxylic acid.
  • preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
  • Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melisic acid, tetraliacontanoic acid, montanic acid, Examples include glutaric acid, adipic acid, and azelaic acid.
  • aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferred.
  • aliphatic also includes alicyclic compounds.
  • alcohol examples include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, etc. be able to.
  • the above ester compound may contain an aliphatic carboxylic acid and/or an alcohol as an impurity, or may be a mixture of a plurality of compounds.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as the main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monostearate.
  • glycerin distearate, glycerin tristearate pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and the like.
  • aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomers having 3 to 12 carbon atoms.
  • aliphatic hydrocarbons also include alicyclic hydrocarbons.
  • these hydrocarbon compounds may be partially oxidized.
  • paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax and polyethylene wax are more preferred.
  • the number average molecular weight is preferably 200 to 5,000.
  • aliphatic hydrocarbons may be a single substance or a mixture of various components and molecular weights, as long as the main components are within the above range.
  • the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.
  • the addition ratio of the mold release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass, based on 100 parts by mass of the thermoplastic resin. The amount is more preferably 1 part by mass or less.
  • One type of mold release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • Colorant may be either a dye or a pigment, and examples thereof include inorganic pigments, organic pigments, and organic dyes.
  • Inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; titanium oxide, zinc white, Bengara, chromium oxide, iron black, titanium yellow, and zinc-iron.
  • Oxide pigments such as brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic acid pigments such as yellow and molybdate orange; ferrocyan such as navy blue Examples include pigments such as pigments.
  • organic pigments and organic dyes used as colorants include phthalocyanine dyes and pigments (dyes or pigments are referred to as dyes and pigments, hereinafter the same) such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; Dyes and pigments; condensed polycyclic dyes and pigments such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, methyl dyes, etc. can be mentioned.
  • phthalocyanine dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green
  • azo dyes such as nickel azo yellow
  • Dyes and pigments condensed polycyclic dyes and pigments such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and
  • the colorant may be masterbatched with polystyrene resin, polycarbonate resin, or acrylic resin for the purpose of improving handling properties during extrusion and dispersibility in the resin composition. good.
  • the addition ratio of the colorant, when blended, is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, and 0. It is 1 part by mass or more.
  • One type of colorant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • thermoplastic resin composition of the present invention may contain a thermoplastic resin other than the above-mentioned polycarbonate-polysilyl ether resin, such as a polycarbonate resin.
  • a thermoplastic resin other than the above-mentioned polycarbonate-polysilyl ether resin such as a polycarbonate resin.
  • polycarbonate resins that do not fall under the above-mentioned thermoplastic resins include polycarbonate resins that completely or substantially do not contain the silyl ether structural unit (B).
  • polycarbonate resins that do not fall under the above-mentioned polycarbonate-polysilyl ether resins
  • -[O-R-OCO]- units containing carbonate ester bonds in the molecular main chain R is an aliphatic group, an aromatic group, It is not particularly limited as long as it contains both an aliphatic group and an aromatic group, or a linear or branched structure.
  • the polycarbonate resin that does not fall under the above-mentioned polycarbonate-polysilyl ether resin may contain polyester carbonate.
  • the polyester carbonate is not particularly limited as long as it is a -[OR-OC]- unit (R is as described above) containing a carbonate bond in the molecular main chain.
  • the weight average molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.
  • the composition of the present invention may contain resins other than polycarbonate-polysilyl ether resins, preferably thermoplastic resins.
  • the type of thermoplastic resin as such a subcomponent is not particularly limited, but in addition to polycarbonate resin and polyester carbonate resin, acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose ( Examples include various resins such as TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide.
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • TAC polyethylene naphthalate
  • PI polyimide
  • COC cycloolefin copolymer
  • norbornene-containing resin polyethersulfone, cellophane, and aromatic polyamide.
  • the proportion of the total weight of silicon atoms (total Si amount) based on the total weight of the composition is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass.
  • the content is more preferably 0.3 to 10% by mass.
  • the proportion of the total amount of Si in the composition depends on the proportion of the silyl ether structural unit (B) in the total structural units in the above-mentioned polycarbonate-polysilyl ether resin, or the amount of resin mixed with the polycarbonate resin and the amount of Si. can be adjusted.
  • a composition with excellent characteristics can be produced using a thermoplastic resin with a high Si content.
  • a thermoplastic resin or the like having a Si content of, for example, 0.1% by mass or more with a resin that does not substantially contain silyl ether structural units, preferably a polycarbonate resin, the resulting composition can be improved. It is possible to achieve both impact resistance and fluidity.
  • a phenol compound that may be produced as a byproduct of a polymerization reaction a silane compound, a carbonate compound, and a diol compound that remain without reacting may be included. Since impurities such as phenolic compounds and diphenyl carbonate may cause a decrease in strength or the generation of odor when molded, the content of these impurities is preferably as low as possible. For this reason, the contents of phenolic compounds, silane compounds, carbonate compounds, and diol compounds may be reduced to such an extent that they are not detected, but from the viewpoint of productivity, they should not be contained in the composition to the extent that their effects are not impaired. You can.
  • the aromatic monohydroxy compound represented by aryl alcohol such as phenol is present in an amount of, for example, more than 300 mass ppm or more, more than 500 mass ppm or more, more than 700 mass ppm or more, May be included.
  • thermoplastic resin or thermoplastic resin composition of the present invention a molded article according to the present invention containing the thermoplastic resin or thermoplastic resin composition of the present invention.
  • the molded article according to the present invention is obtained by molding the above-mentioned thermoplastic resin or a composition containing the thermoplastic resin.
  • the method for forming the molded product is not particularly limited, and examples of the molded product include injection molded products, press molded products, blow molded products, extrusion molded products, vacuum molded products, and pressure molded products.
  • the molded article of the present invention is, for example, a film such as an optical film.
  • the thermoplastic resin of the present invention is suitable for optical applications, and optical films have particularly excellent properties.
  • the molded article of the present invention may also include an optical lens, and such an optical lens has a refractive index, Abbe number, etc. within an appropriate range.
  • Tg glass transition temperature
  • the temperature of the measurement sample adjusted to 30°C was raised to 280°C at a rate of 20°C/min, and then cooled to 30°C at a rate of 20°C/min. Thereafter, the temperature was raised to 280°C at a rate of 10°C/min and measurements were taken.
  • thermoplastic resins with a Tg measured by the above method of 50°C or more and 150°C or less and a Q value of 3 or more at 240°C are considered good, and either Tg or Q value Comparative examples that did not meet the requirements were determined to be defective.
  • YI value (yellowness)> The YI value indicates the degree to which the hue deviates from colorless or white toward yellow (yellowness).
  • ⁇ GC/FID measurement conditions The conditions for the above GC/FID measurement are as follows. ⁇ Device: GC2025 manufactured by Shimadzu Corporation ⁇ Column: Capillary column DB-35, 30mm x 0.25mm x 0.25 ⁇ m ⁇ Temperature rising conditions: 40°C-300°C (3min hold), 20°C/min ⁇ Inlet temperature: 300°C, injection amount: 1.0 ⁇ L (split ratio 1:20) ⁇ Carrier gas: He ⁇ Air flow rate: 400mL/min ⁇ H2 flow rate: 40mL/min ⁇ Makeup gas: 30mL/min
  • Mn ⁇ (W i )/ ⁇ (W i /M i )
  • Mw ⁇ (W i ⁇ M i )/ ⁇ (W i )
  • i represents the i-th division point when dividing the molecular weight M
  • W i represents the i-th weight
  • M i represents the i-th molecular weight.
  • the molecular weight M is the same elution point of the calibration curve.
  • integral value of the signal originating from the isosorbide bound with 4.70 ppm to 4.85 ppm of carbonate is determined and is defined as integral value (1).
  • integral value of the signal originating from the phenyl end derived from the carbonate bond from 7.35 ppm to 7.45 ppm is determined and is defined as integral value (2).
  • integral value of the signal derived from the phenyl end derived from the dimethylsilyl ether bond from 6.95 ppm to 7.20 ppm is determined and is defined as integral value (3).
  • integral value of the signal originating from the double bond of the structure in which isosorbide is dehydrated from 6.60 ppm to 6.63 ppm is determined and is defined as integral value (4).
  • Formula weight of isosorbide unit linked with carbonate 172.1
  • Formula weight of isosorbide unit bonded with dimethylsilyl ether group 202.3
  • Formula weight of phenyl terminal unit derived from carbonate bond 94.1
  • Formula weight of phenyl terminal unit derived from dimethylsilyl ether bond 94.1
  • Formula weight of isosorbide double bond terminal unit 155.13
  • Example 1 28.0 g of isosorbide, 36.1 g of diphenyl carbonate, 8.0 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide). (number of moles) was placed in a 300 ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction proceeded while condensing and removing phenol distilled from the reaction system using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 240°C.
  • the pressure was reduced to 50 hPa and the reaction was allowed to proceed for 5 minutes, the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was 34,805.
  • Example 2 27.9 g of isosorbide, 36.0 g of diphenyl carbonate, 8.5 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide).
  • 0.034 g of ⁇ ADEKA STAB PEP-36'' manufactured by ADEKA Co., Ltd. as a phosphite-based antioxidant was placed in a 300 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere.
  • the raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes. At this time, the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube. Next, the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 240°C.
  • Example 3 27.9 g of isosorbide, 33.1 g of diphenyl carbonate, 12.0 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide).
  • 0.034 g of "ADEKA STAB PEP-36" manufactured by ADEKA Co., Ltd. as an antioxidant was placed in a 300 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with nitrogen atmosphere.
  • the raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes. At this time, the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube. Next, the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 240°C.
  • Example 4 27.9 g of isosorbide, 33.1 g of diphenyl carbonate, 12.0 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide). (number of moles) was placed in a 300 ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction proceeded while condensing and removing phenol distilled from the reaction system using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 240°C.
  • the pressure was reduced to 50 hPa and the reaction was allowed to proceed for 5 minutes, the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was 37,028.
  • Example 5 27.9 g of isosorbide, 24.5 g of diphenyl carbonate, 23.0 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide). (number of moles) was placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 220°C.
  • the pressure was reduced to 50 hPa and the reaction was allowed to proceed for 5 minutes, the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was found to be 21,536.
  • Example 6 1872.3 g of isosorbide, 2223.2 g of diphenyl carbonate, 880.1 g of dimethyldiphenoxysilane, and 6.0 ⁇ mol/mol of sodium bicarbonate and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide).
  • ADEKA STAB PEP-36 manufactured by ADEKA Co., Ltd. as an antioxidant was placed in a 10 liter reactor equipped with a stirrer, the inside of the system was replaced with a nitrogen atmosphere, and the pressure was reduced to 500 hPa.
  • the raw materials were melted by heating at 190°C, and after reacting for 30 minutes, the pressure was reduced to 190 hPa, the temperature was raised to 195°C, and the reaction was carried out for 30 minutes. At this time, the reaction proceeded while condensing and removing phenol distilled from the reaction system using a cooling tube. Next, the temperature was raised to 200°C for 30 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 220°C.
  • Example 7 1872.3 g of isosorbide, 2412.8 g of diphenyl carbonate, 570.6 g of dimethyldiphenoxysilane, and 6.0 ⁇ mol/mol of sodium bicarbonate and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (catalyst amounts are relative to isosorbide).
  • 4.770 g of "ADEKA STAB PEP-36" manufactured by ADEKA Co., Ltd. as an antioxidant was placed in a 10-liter reactor equipped with a stirrer, and the system was replaced with a nitrogen atmosphere and the pressure was reduced to 500 hPa.
  • the raw materials were melted by heating at 190°C, and after reacting for 30 minutes, the pressure was reduced to 190 hPa, the temperature was raised to 195°C, and the reaction was carried out for 30 minutes. At this time, the reaction proceeded while condensing and removing phenol distilled from the reaction system using a cooling tube. Next, the temperature was raised to 200°C for 30 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 220°C.
  • the reaction was started for 10 minutes, the pressure was reduced to 50 hPa and the temperature was raised to 240° C., the reaction was continued for 10 minutes, and then the pressure was reduced to less than 1 hPa and the reaction was carried out for 60 minutes.
  • the Mw was found to be 41,313.
  • Example 8 1698.9 g of isosorbide, 266.3 g of spiroglycol, 2253.4 g of diphenyl carbonate, 724.7 g of dimethyldiphenoxysilane, and 6.0 ⁇ mol/mol of sodium bicarbonate and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide (catalyst). (the amount is relative mole number to the total mole amount of all diols) was placed in a 10 L reactor equipped with a stirrer, the pressure inside the reactor was set to less than 1 hPa, and the raw material was dried for 30 minutes. Next, the inside of the system was replaced with a nitrogen atmosphere.
  • the raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200 °C for 15 minutes, the temperature was raised to 205 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 160 hPa, the temperature was raised to 210 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 100 hPa, and the temperature was started to increase to 240 °C.
  • the Mw was 48,184.
  • Example 9 1552.7 g of isosorbide, 570.7 g of spiroglycol, 2455.3 g of diphenyl carbonate, 416.3 g of dimethyldiphenoxysilane, and 6.0 ⁇ mol/mol of sodium bicarbonate and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide (catalyst). (the amount is relative mole number to the total mole amount of all diols) was placed in a 10 L reactor equipped with a stirrer, the pressure inside the reactor was set to less than 1 hPa, and the raw material was dried for 30 minutes. Next, the inside of the system was replaced with a nitrogen atmosphere.
  • the raw materials were heated and melted at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200 °C for 15 minutes, the temperature was raised to 205 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 160 hPa, the temperature was raised to 210 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 100 hPa, and the temperature was started to increase to 240 °C.
  • the pressure was reduced to 50 hPa, and the reaction was carried out for 10 minutes.
  • Example 10 42.4 g of isosorbide, 27.9 g of spiroglycol, 74.7 g of diphenyl carbonate, 12.7 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of magnesium acetate, 3.0 ⁇ mol/mol of calcium acetate and tetraphenylphosphonium phenoxide as catalysts.
  • 1.0 ⁇ mol/mol (the amount of catalyst is the number of moles relative to the total mole amount of all diols) was placed in a 300 ml four-necked flask equipped with a stirrer, the pressure inside the flask was set to less than 1 hPa, and the raw material was dried for 30 minutes. did.
  • the inside of the system was replaced with a nitrogen atmosphere.
  • the raw materials were heated and melted at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature started to rise to 240°C.
  • the pressure was reduced to 50 hPa, and after reaction for 5 minutes, the pressure was reduced to less than 1 hPa, and the reaction was carried out for 50 minutes.
  • the Mw was found to be 34,087.
  • Example 11 1552.7 g of isosorbide, 570.7 g of spiroglycol, 2253.4 g of diphenyl carbonate, 724.7 g of dimethyldiphenoxysilane, and 6.0 ⁇ mol/mol of sodium bicarbonate and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide (catalyst). (the amount is relative mole number to the total mole amount of all diols) was placed in a 10 L reactor equipped with a stirrer, the pressure inside the reactor was set to less than 1 hPa, and the raw material was dried for 30 minutes. Next, the inside of the system was replaced with a nitrogen atmosphere.
  • the raw materials were heated and melted at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200 °C for 15 minutes, the temperature was raised to 205 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 160 hPa, the temperature was raised to 210 °C, and the reaction was performed for 20 minutes, the pressure was reduced to 100 hPa, and the temperature was started to increase to 240 °C.
  • the Mw was 55,615.
  • Example 12 58.9 g of isosorbide, 78.7 g of diphenyl carbonate, 13.4 g of diphenyldimethoxysilane, and 3.0 ⁇ mol/mol of magnesium acetate, 3.0 ⁇ mol/mol of calcium acetate, and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide (catalyst).
  • the amount is relative mole number to the total mole amount of all diols
  • the raw materials were heated and melted at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature started to rise to 240°C.
  • the pressure was reduced to 50 hPa, and the reaction was carried out for 5 minutes.
  • the pressure was then reduced to less than 1 hPa, and the reaction was carried out for 50 minutes.
  • the Mw was found to be 22,530.
  • Example 13 58.9 g of isosorbide, 78.7 g of diphenyl carbonate, 10.0 g of dimethoxymethylphenylsilane, and 3.0 ⁇ mol/mol of magnesium acetate as a catalyst, 3.0 ⁇ mol/mol of calcium acetate, and 1.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide (The catalyst amount (the number of moles relative to the total mole amount of all diols) was placed in a 300 ml four-necked flask equipped with a stirrer, the pressure inside the flask was set to less than 1 hPa, and the raw material was dried for 30 minutes. Next, the inside of the system was replaced with a nitrogen atmosphere.
  • the catalyst amount (the number of moles relative to the total mole amount of all diols) was placed in a 300 ml four-necked flask equipped with a stirrer, the pressure inside the flask was set to less than 1
  • the raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was allowed to proceed for 30 minutes, and the reaction proceeded while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature started to rise to 240°C.
  • the pressure was reduced to 50 hPa and the reaction was carried out for 5 minutes, and then the pressure was reduced to less than 1 hPa and the reaction was carried out for 60 minutes.
  • the Mw was found to be 26,656.
  • Comparative example 1 27.9 g of isosorbide, 42.0 g of diphenyl carbonate, and 3.0 ⁇ mol/mol of sodium hydrogen carbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (the amount of catalyst is the number of moles relative to isosorbide) were prepared using a stirrer. The mixture was placed in a 300 ml four-necked flask, and the inside of the system was purged with nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction proceeded while condensing and removing phenol distilled from the reaction system using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 210°C and reacted for 10 minutes, the pressure was reduced to 100hPa, and the temperature was raised to 240°C.
  • the pressure was reduced to 50 hPa and the reaction was allowed to proceed for 5 minutes, the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was 25,564.
  • Comparative example 2 55.8 g of isosorbide, 99.5 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (the amount of catalyst is the number of moles relative to isosorbide) were added to a stirrer. The mixture was placed in a 300 ml four-necked flask equipped with a nitrogen atmosphere, and the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200 °C for 15 minutes, the temperature was raised to 205 °C, and reaction was performed for 20 minutes, the pressure was reduced to 160 hPa, the temperature was started to be raised to 210 °C, and the reaction was performed for 10 minutes, the pressure was reduced to 100 hPa, and the reaction was performed for 5 minutes, After reducing the pressure to 50 hPa and reacting for 5 minutes, the pressure was reduced to less than 1 hPa and heating to 220° C. was started, and the reaction was carried out for 90 minutes.
  • the Mw was found to be 20,873.
  • Comparative example 3 18.9 g of isosorbide, 18.9 g of spiroglycol, 42.7 g of diphenyl carbonate, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (the catalyst amounts are relative moles to isosorbide). ) was placed in a 300 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 200°C for 15 minutes, the temperature was raised to 205°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was started to be raised to 210°C, the reaction was carried out for 10 minutes, and the pressure was reduced to 100hPa.
  • the temperature was raised to 240° C. and the reaction was carried out for 5 minutes, the pressure was reduced to 50 hPa and the reaction was carried out for 5 minutes, and the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was found to be 37,724.
  • Comparative example 4 27.9 g of isosorbide, 11.0 g of diphenyl carbonate, 38.0 g of dimethyldiphenoxysilane, and 3.0 ⁇ mol/mol of sodium bicarbonate and 3.0 ⁇ mol/mol of tetraphenylphosphonium phenoxide as catalysts (each catalyst amount is relative to isosorbide). (number of moles) was placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with nitrogen atmosphere. The raw materials were melted by heating at 195° C., and after reacting for 30 minutes, the pressure was reduced to 190 hPa and the reaction was continued for an additional 30 minutes.
  • the reaction was allowed to proceed while the phenol distilled from the reaction system was coagulated and removed using a cooling tube.
  • the temperature was raised to 210°C for 15 minutes, the temperature was raised to 215°C and reacted for 20 minutes, the pressure was reduced to 160hPa, the temperature was raised to 220°C and reacted for 10 minutes, the pressure was reduced to 100hPa and the temperature was reacted for 5 minutes, and the pressure was reduced to 50hPa. After reducing the pressure and reacting for 5 minutes, the pressure was reduced to less than 1 hPa and the reaction was carried out for 50 minutes.
  • the Mw was found to be 12,731.
  • thermoplastic resin of each Example and Comparative Example are as shown in Table 2 below. Furthermore, the structural units contained in the resins obtained in each Example and Comparative Example are as shown in the margins of Table 2.
  • the glass transition temperature (Tg) value was as low as 3.8°C, which was below room temperature, so it was difficult to introduce it into an apparatus for measuring the Q value. It was not possible to make a film for sex testing. Therefore, although it can be said that the results were unfavorable for these evaluation items, Table 2 shows that each item was not measurable or evaluable. In addition, in Comparative Example 4, although it was possible to form a film, the film melted under the chemical resistance test conditions, and although it can be said that this was an unfavorable result, Table 2 shows that it cannot be evaluated.
  • thermoplastic resin composition of the present invention has high moldability, as well as excellent hue, chemical resistance, and the like. Furthermore, the thermoplastic resin composition of the present invention is expected to be suitably used as a material for a high hardness resin layer. Further, the thermoplastic resin composition of the present invention containing Si element at the silyl ether bonding site is considered to have excellent flame retardancy. Furthermore, the thermoplastic resin composition of the present invention having an isosorbide skeleton can exhibit high strength, and can improve various mechanical strengths when producing molded articles.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232897A (ja) * 2005-02-22 2006-09-07 Mitsubishi Gas Chem Co Inc コポリカーボネート樹脂
WO2008020636A1 (en) * 2006-08-18 2008-02-21 Mitsubishi Gas Chemical Company, Inc. Polycarbonate resin and optical film using the same
WO2020196343A1 (ja) * 2019-03-22 2020-10-01 三菱瓦斯化学株式会社 ポリカーボネート共重合体及びポリシロキサン化合物の製造方法、ポリカーボネート共重合体、ポリシロキサン化合物、組成物、及び、成形体
WO2021112260A1 (ja) * 2019-12-06 2021-06-10 出光興産株式会社 ポリカーボネート－ポリオルガノシロキサン共重合体及び該共重合体を含む樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232897A (ja) * 2005-02-22 2006-09-07 Mitsubishi Gas Chem Co Inc コポリカーボネート樹脂
WO2008020636A1 (en) * 2006-08-18 2008-02-21 Mitsubishi Gas Chemical Company, Inc. Polycarbonate resin and optical film using the same
WO2020196343A1 (ja) * 2019-03-22 2020-10-01 三菱瓦斯化学株式会社 ポリカーボネート共重合体及びポリシロキサン化合物の製造方法、ポリカーボネート共重合体、ポリシロキサン化合物、組成物、及び、成形体
WO2021112260A1 (ja) * 2019-12-06 2021-06-10 出光興産株式会社 ポリカーボネート－ポリオルガノシロキサン共重合体及び該共重合体を含む樹脂組成物

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