WO2022065329A1 - 熱可塑性樹脂、組成物、成形体、光学レンズ、及び、熱可塑性樹脂の製造方法 - Google Patents

熱可塑性樹脂、組成物、成形体、光学レンズ、及び、熱可塑性樹脂の製造方法 Download PDF

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WO2022065329A1
WO2022065329A1 PCT/JP2021/034678 JP2021034678W WO2022065329A1 WO 2022065329 A1 WO2022065329 A1 WO 2022065329A1 JP 2021034678 W JP2021034678 W JP 2021034678W WO 2022065329 A1 WO2022065329 A1 WO 2022065329A1
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group
substituent
thermoplastic resin
carbon atoms
compound
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English (en)
French (fr)
Japanese (ja)
Inventor
大輔 田口
康平 釜谷
宣人 秋元
和良 上等
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to KR1020237011758A priority Critical patent/KR20230071149A/ko
Priority to EP21872458.1A priority patent/EP4219589A4/en
Priority to JP2022552011A priority patent/JPWO2022065329A1/ja
Priority to CN202180064492.9A priority patent/CN116390968A/zh
Priority to US18/027,164 priority patent/US20230331925A1/en
Publication of WO2022065329A1 publication Critical patent/WO2022065329A1/ja
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
    • 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
    • C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C08G77/52—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the present invention relates to a thermoplastic resin, a composition containing a thermoplastic resin, a method for producing a thermoplastic resin, and the like.
  • Thermoplastic resins are formed into various molded products by a simple and highly productive processing method such as injection molding, and are used in a wide range of industrial fields such as electrical and electronic, OA equipment, heavy electrical machinery, precision machinery, and automobile fields. There is. However, in the conventional thermoplastic resin, sufficiently high heat resistance and flame retardancy are not always realized. Conventional thermoplastic resins may be inferior in chemical resistance.
  • polysiloxane As a material for a molded product, a polymer of aromatic polysiloxane, which is also called polyarylene siloxane, is known (for example, Patent Document 1).
  • polysiloxane compounds such as polyarylene siloxane
  • polyarylene siloxane is used, for example, as a release layer in photographic copying, a photoresist material, a plasticizer for polycarbonate, a component of a powder surface coating system, and the like. It is used as.
  • Polysiloxane compounds such as polyarylene siloxanes tend to have relatively high heat resistance and flame retardancy, but their performance is not always sufficiently excellent. Further, as a method for producing a polysiloxane compound, a method in which hydrochloric acid is generated to react with dimethyldichlorosilane and bisphenol A in a solvent (Non-Patent Document 1), and a method in which the reaction is carried out in a solvent to which acetic acid is added (Patent Document 2). ) Etc. are known, but it is desired to ensure safety.
  • thermoplastic resins, polysiloxane compounds, etc. that are particularly suitable for specific applications such as optical applications have not always been realized so far.
  • thermoplastic resin having a siloxane constituent unit having excellent heat resistance and flame retardancy particularly a thermoplastic resin suitable for optical applications, a composition containing such a thermoplastic resin, and the like.
  • thermoplastic resin having a siloxane constituent unit provides a safe and efficient manufacturing method of a thermoplastic resin having a siloxane constituent unit. That is, a method for efficiently producing a thermoplastic resin having a siloxane constituent unit while making it possible to reduce the environmental load without producing corrosive substances such as hydrochloric acid and acetic acid and without using a solvent. offer.
  • the present invention provides the thermoplastic resin described below, a composition containing the thermoplastic resin, a molded product, and the like, which contain a siloxane constituent unit and have excellent heat resistance and flame retardancy.
  • the present invention also provides a method for producing a thermoplastic resin containing a siloxane constituent unit.
  • the production method of the present invention does not generate by-products having a high environmental load such as acid, and can be carried out without a solvent, particularly without a solvent requiring consideration for safety.
  • Each of R a to R d independently has a hydrogen atom, a halogen atom, an alkyl group having a total carbon number of 1 to 20 which may have a substituent, or an alkyl group having a total carbon number of 6 to 20 which may have a substituent.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • m represents an integer of 1 to 3.
  • the above [1] containing at least one of the structural units (B-1) to (B-4) represented by any of the following general formulas (II-1) to (II-4).
  • the thermoplastic resin described in. In the general formulas (II-1) to (II-4), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • R 3 to R 10 , R 21 to R 26 , and R 31 to R 36 are independent hydrogen atoms, respectively.
  • Z 1 and Z 2 are alkylene groups having 1 to 5 carbon atoms which may independently have a substituent.
  • J 1 represents an integer from 0 to 5 independently of each other.
  • K 1 represents an integer from 0 to 5 independently of each other.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • a 1 and A 2 independently represent either -O- or -CH 2- .
  • L 1 and L 2 each independently represent an integer of 0 to 3.
  • X is either a single bond or any of the structural formulas represented by the following formulas (1) to (7). (In the general formulas (1) to (7), R 11 and R 12 each independently have a hydrogen atom, a halogen atom, 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.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • r and s each independently represent an integer from 0 to 5000.
  • the molar ratio of the structural unit (A) to the total of the structural units (B-1) to (B-4) is 0.1: 99.9 to 100: 0, as described above [1]. ]
  • thermoplastic resin according to any one of [3].
  • R 3 to R 10 , R 21 to R 26 , and R 31 to R 36 independently have a hydrogen atom, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, which may have a substituent, and a substituent.
  • Z 1 and Z 2 are alkylene groups having 1 to 5 carbon atoms which may independently have a substituent.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • J 1 represents an integer from 0 to 5 independently of each other.
  • K 1 represents an integer from 0 to 5 independently of each other.
  • a 1 and A 2 independently represent either -O- or -CH 2- .
  • L 1 and L 2 each independently represent an integer of 0 to 3.
  • X is either a single bond or any of the structural formulas represented by the following formulas (1) to (7).
  • R 11 and R 12 each independently have a hydrogen atom, a halogen atom, 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.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • r and s each independently represent an integer from 0 to 5000.
  • the molar ratio of the total of the structural units (A) and the structural units (B-1) to (B-4) to the total of the structural units (C-1) to (C-4) is The thermoplastic resin according to the above [4], which is 0.1: 99.9 to 100: 0.
  • the thermoplastic resin according to the above [1] which comprises only the structural unit (A).
  • Mw polystyrene-equivalent weight average molecular weight
  • thermoplastic resin according to any one of the above [1] to [12] and a polycarbonate resin.
  • Q1 which is a Q value measured under the condition of 280 ° C. and 160 kgf in the composition is 120 of Q2 which is a Q value measured only by the polycarbonate resin contained in the composition under the same conditions. % Or more, the composition according to the above [13].
  • a diaryloxysilane compound which is one of a dialkyldiaryloxysilane, adiaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, and a dialkyldialkoxysilane, adiaryldialkoxysilane, and a monoalkylmonoaryldi.
  • Each of R a to R d independently has a hydrogen atom, a halogen atom, an alkyl group having a total carbon number of 1 to 20 which may have a substituent, or an alkyl group having a total carbon number of 6 to 20 which may have a substituent.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • m represents an integer of 1 to 3.
  • a method for producing a thermoplastic resin which comprises producing a thermoplastic resin containing a structural unit (A) represented by the following general formula (I).
  • Each of R a to R d independently has a hydrogen atom, a halogen atom, an alkyl group having a total carbon number of 1 to 20 which may have a substituent, or an alkyl group having a total carbon number of 6 to 20 which may have a substituent.
  • the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.
  • thermoplastic resin according to the above [17] wherein a catalyst containing an alkali metal compound and / or an alkaline earth metal compound is used in the polymerization step.
  • a catalyst containing an alkali metal compound and / or an alkaline earth metal compound is used in the polymerization step.
  • Re independently represents an alkyl group, an aryl group, or an alkylaryl group, and a plurality of Res may be bonded to each other to form a ring structure.
  • Xc is a hydroxyl group, a halogen atom, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BRf 4 (Rf is a hydrogen atom, an alkyl group, or an aryl group, respectively. Is).
  • thermoplastic resin according to any one of [17] to [21] above, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000.
  • the amount of the catalyst used in the polymerization step with respect to the diol compound is 1.0 ⁇ 10 -7 to 1.0 ⁇ 10-2 in terms of molar ratio.
  • the reaction temperature in the polymerization step is in the range of 150 ° C. or higher and 300 ° C. or lower.
  • thermoplastic resin according to any one of [17] to [24] above further comprising a depressurizing step of gradually reducing the reaction pressure from 24,000 Pa or more to less than 100 Pa in the polymerization step. ..
  • a depressurizing step of gradually reducing the reaction pressure from 24,000 Pa or more to less than 100 Pa in the polymerization step.
  • oxysilane compound and the diol compound are polymerized under a pressure of less than 100 Pa.
  • thermoplastic resin Described in any one of [17] to [27], wherein the ratio of the number of moles of the oxysilane compound used in the polymerization step to the number of moles of the diol compound is 0.9 or more and 1.2 or less.
  • Method for manufacturing thermoplastic resin [29] A molecular weight measuring step for measuring the molecular weight of the thermoplastic resin produced in the polymerization step, and a molecular weight measuring step. The method for producing a thermoplastic resin according to any one of [17] to [28], further comprising an additional polymerization step of repolymerizing the thermoplastic resin having a molecular weight lower than a predetermined target value.
  • thermoplastic resin having a siloxane constituent unit having excellent heat resistance and flame retardancy particularly a thermoplastic resin suitable for optical applications, and a composition or a molded body containing such a thermoplastic resin can be obtained. realizable. Further, according to the present invention, a thermoplastic resin or the like having a siloxane constituent unit can be produced by a safe and efficient production method.
  • thermoplastic resin of the present invention will be described in detail.
  • Thermoplastic resin of the present invention is a polymer having a siloxane structural unit, and specifically contains at least the structural unit (A) represented by the following formula (I).
  • Ra to R d each independently have a hydrogen atom, a halogen atom, an alkyl group having a total carbon number of 1 to 20 and may have a substituent, or a substituent. It also represents an aryl group having a total carbon number of 6 to 30.
  • the total number of carbon atoms of the alkyl group which may have a substituent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the total number of carbon atoms of the aryl group which may have a substituent is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12.
  • R a to R d are preferably a hydrogen atom, an alkyl group having a total carbon number of 1 to 20 which may have a substituent, or an aryl group having a total carbon number of 6 to 30 which may have a substituent. Yes, more preferably a hydrogen atom.
  • Xa and Xb are each independently an alkyl group having a total carbon number of 1 to 20 which may have a substituent, or an alkyl group having a total carbon number of 6 to 30 which may have a substituent.
  • the total number of carbon atoms of the alkyl group and the aryl group is the same as that of Ra to R d .
  • Xa and Xb are preferably an alkyl group having a total carbon number of 1 to 20 and may have a hydrogen atom or a substituent, and more preferably a hydrogen atom or an alkyl group having a total carbon number of 1 to 5. It is a group, particularly preferably a methyl group.
  • the above-mentioned substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group and an alkoxy group, and the total carbon number of the alkenyl group and the alkynyl group is preferably 2 to 10. It is preferably 2 to 5, and the total number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 5.
  • thermoplastic resin as represented by the formula (I), the-(O [Ph (Ra-d)] m-site and the-(OSi (Xa) (Xb)-) moiety are alternately repeated. It is preferable that the thermoplastic resin contains a structural unit. As described above, the thermoplastic resin has a large number of-(O [Ph (Ra to d)] m-sites, repeated portions, and-(OSi (Xa) (Xb)-). ) It is preferable to use a random copolymer rather than a block copolymer containing a portion in which only the moiety is repeated many times.
  • thermoplastic resin in the following general formula (Ia), the number of alternating repetitions of the-(O [Ph (Ra-d)] m-site and the-(OSi (Xa) (Xb)-) moiety is repeated. It is preferable to have a structural unit in which the value of n shown is preferably 10 or more, more preferably 20 or more, further preferably 30 or more, still more preferably 50 or more, and particularly preferably 100 or more.
  • the thermoplastic resin has many regions in which the-(O [Ph (Ra to d)] m-site and the-(OSi (Xa) (Xb)-) moiety are alternately connected, and is random.
  • the thermoplastic resin obtained by copolymerization is easier to form char at high temperatures, and tends to be excellent in heat resistance and flame retardancy.
  • thermoplastic resin may be composed of only the above-mentioned structural unit (A), but may have other structural units.
  • additional structural unit of the thermoplastic resin at least one of the structural units (B-1) to (B-4) represented by the general formulas (II-1) to (II-4) can be mentioned.
  • R 1 and R 2 each independently have an alkyl group having 1 to 20 carbon atoms or a substituent which may have a substituent. It represents an aryl group having 6 to 30 carbon atoms which may be used.
  • the total number of carbon atoms of the alkyl group which may have a substituent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 5.
  • the total number of carbon atoms of the aryl group which may have a substituent is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12.
  • R 3 to R 10 , R 21 to R 26 , and R 31 to R 36 each independently have a hydrogen atom, a halogen atom, and a substituent.
  • An alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent may be used. It is an aryl group having 6 to 30 carbon atoms which may be possessed.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are alkyl groups which may have a substituent, the total number of carbon atoms is preferably 1 to 10, and the total number of carbon atoms is preferably 1 to 10. It is more preferably 1 to 4, and particularly preferably 1 or 2 in total carbon number.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are alkenyl groups which may have a substituent, the total carbon number is preferably 2 to 10, and the total carbon number is 2. It is more preferably 2 to 6, and particularly preferably the total number of carbon atoms is 2 to 4.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are aryl groups which may have a substituent
  • the total carbon number is preferably 6 to 20, and the total carbon number is preferably 6 to 20.
  • the number is more preferably 6 to 12, and the total number of carbon atoms is particularly preferably 6 to 8.
  • Z 1 and Z 2 are alkylene groups having 1 to 5 carbon atoms which may independently have a substituent.
  • Z 1 and Z 2 are preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms.
  • J 1 independently represents an integer of 0 to 5
  • K 1 independently represents an integer of 0 to 5.
  • J 1 and K 1 each independently represent an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less, for example, 1 or 2. ..
  • a 1 and A 2 are independently one of -O- and -CH 2- .
  • L 1 and L 2 are independently integers of 0 to 3.
  • L 1 and L 2 are preferably 1 or 2.
  • the above-mentioned substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group and an alkoxy group, and the total number of carbon atoms of the alkenyl group and the alkynyl group is , Preferably 2 to 10, more preferably 2 to 5, and the total number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 5.
  • X is either a single bond or a structural formula represented by the following formulas (1) to (7).
  • R 11 and R 12 each independently have a hydrogen atom, a halogen atom, and an alkyl group having a total carbon number of 1 to 20 or a substituent which may have a substituent.
  • the total number of carbon atoms of the alkyl group which may have a substituent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 5.
  • the total number of carbon atoms of the aryl group which may have a substituent is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12.
  • the above-mentioned substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group and an alkoxy group.
  • r and s are independently integers of 0 to 5000, preferably 0 to 1000, and more preferably 0 to 500.
  • the structural units (B-1) to (B-4) represented by the general formulas (II-1) to (II-4) can be added at any ratio to the structural unit (A).
  • the molar ratio of a: b is preferably 10:90 to 95: 5, more preferably 20:80 to 90:10, still more preferably 30:70 to 80:20, and particularly preferably. , 30: 70 to 70:30.
  • thermoplastic resin is composed of at least one of the above-mentioned structural units (A) and (B-1) to (B-4), for example, only the structural units (A) and (B-1). It may have other building blocks.
  • the structural units (C-1) to (C-4) represented by the general formulas (III-1) to (III-4) can be mentioned.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 each independently have a hydrogen atom, a halogen atom and a substituent.
  • An alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent may be used. It is an aryl group having 6 to 30 carbon atoms which may be possessed.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are alkyl groups which may have a substituent, the total number of carbon atoms is preferably 1 to 10, and the total number of carbon atoms is preferably 1 to 10. It is more preferably 1 to 4, and particularly preferably 1 or 2 in total carbon number.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are alkenyl groups which may have a substituent, the total carbon number is preferably 2 to 10, and the total carbon number is 2. It is more preferably 2 to 6, and particularly preferably the total number of carbon atoms is 2 to 4.
  • R 3 to R 10 , R 21 to R 26 and R 31 to R 36 are aryl groups which may have a substituent
  • the total carbon number is preferably 6 to 20, and the total carbon number is preferably 6 to 20.
  • the number is more preferably 6 to 12, and the total number of carbon atoms is particularly preferably 6 to 8.
  • the above-mentioned substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group and an alkoxy group, and the total number of carbon atoms of the alkenyl group and the alkynyl group is , Preferably 2 to 10, more preferably 2 to 5, and the total number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 5.
  • Z 1 and Z 2 are alkylene groups having 1 to 5 carbon atoms which may independently have a substituent.
  • Z 1 and Z 2 are preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms.
  • J 1 independently represents an integer of 0 to 5
  • K 1 independently represents an integer of 0 to 5.
  • J 1 and K 1 each independently represent an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less, for example, 1 or 2. ..
  • a 1 and A 2 are independently one of -O- and -CH 2- . Further, L 1 and L 2 are independently integers of 0 to 3. L 1 and L 2 are preferably 1 or 2.
  • X is either a single bond or a structural formula represented by the following formulas (1) to (7).
  • the above formulas (1) to (7) are synonymous with the formulas (1) to (7) in the general formulas (II-1) to (II-2).
  • C-4) can be added at any rate.
  • the molar ratio of (a + b): c is preferably 10:90 to 95: 5, more preferably 20:80 to 90:10, still more preferably 30:70 to 80:20, and in particular. It is preferably 30:70 to 70:30.
  • thermoplastic resin of the present invention may contain a resin other than the thermoplastic resin of the present invention, if necessary, as long as the desired physical properties are not significantly impaired.
  • other resins include polycarbonate resins other than the thermoplastic resin of the present invention, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate resin (PTT resin), polybutylene terephthalate resin (PBT resin), and the like.
  • Thermoplastic polyester resin such as polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin); methyl methacrylate -Acrylic rubber-Core / shell type elastomer such as styrene copolymer (MAS), elastomer such as polyester elastomer; polyolefin resin such as cyclic cycloolefin resin (COP resin), cyclic cycloolefin (COP) copolymer resin Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin ( PSU resin); polymethacrylate resin (P
  • the weight average molecular weight (Mw) of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 10,000 to 200,000, and preferably 15,000 to 100,000. It is more preferably, for example, 20,000 to 80,000, still more preferably 30,000 to 70,000, and particularly preferably 40,000 to 65,000. As described above, the lower limit of the weight average molecular weight of the thermoplastic resin is preferably 10,000, more preferably 15,000, and even more preferably 20,000.
  • thermoplastic resin As a composition mixed with other resins instead of using it as it is, it may be preferable to significantly increase the ratio of the above-mentioned siloxane constituent unit (A).
  • a thermoplastic resin having a ratio of the above-mentioned siloxane constituent unit (A) of 30% or more, 50% or more, or 70% or more and having a high Si content has a Si or siloxane composition as described in detail later.
  • the upper limit of the ratio of the siloxane constituent unit (A) described above is not limited to 90%, and is, for example, 92%, 95%, 98%, or the like. It may be.
  • the glass transition temperature (Tg) according to JIS K7121 is, for example, ⁇ 30 to 130 ° C., preferably ⁇ 20 to 120 ° C., and more preferably ⁇ 10 to 100 ° C. preferable.
  • the low molecular weight compound having a weight average molecular weight of 1,000 or less is preferably 1% by weight or less, more preferably 0.5% by weight or less, and 0.2% by weight or less. Is more preferable.
  • Thermoplastic resins containing a large amount of low molecular weight compounds having a weight average molecular weight of 1,000 or less are relatively fast when continuously subjected to injection molding for manufacturing discs and complicated and thinned products. At the stage, the mold tends to be contaminated with a small amount of deposit (mold deposit). In this respect, in the thermoplastic resin, if the amount of the low molecular weight compound having a weight average molecular weight of 1,000 or less is 1% by mass or less, contamination of the mold is effectively prevented.
  • the lower limit of the content of the low molecular weight compound having a weight average molecular weight of 1,000 or less in the thermoplastic resin is not particularly important, but is, for example, 0.001% by weight, 0.01% by weight, or 0.1. It may be% by weight.
  • the content of the above-mentioned low molecular weight compound in the thermoplastic resin is a value calculated by summing up the contents of several kinds of low molecular weight compounds which are impurities from the ratio of the peak areas of each component obtained by GPC analysis. .. That is, the proportion of the low molecular weight compound having a molecular weight (weight average molecular weight) of 1,000 or less in the thermoplastic resin is an area with a retention time of 20.5 min to 21.5 min / 0 min to 21. It is a value calculated from the ratio of the area up to 5 min.
  • the total content of the annular bodies represented by the following formulas (5-1) to (5-3) is 4.0% by weight or less based on the total weight of the thermoplastic resin. Is preferable, more preferably 3.0% by weight or less, further preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less. As long as the content of these cyclic dimers is within the above range, it can be said that there is no problem in the properties of the thermoplastic resin, particularly when it is used in optical applications.
  • m and n are the total number of structural units including the (-OSi (R 1 R 2 ) O-) site in each annular body, respectively, and (-).
  • m and n indicate the total number of building blocks of the building blocks represented by the equation, respectively.
  • m represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.
  • n represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.
  • the value of m, that is, the total number of structural units including the (-OSi (R 1 R 2 ) O-) site in the ring is 1 to 10
  • n that is, the ring.
  • m and n are preferably 1 to 5, more preferably 1 or 2, and even more preferably 1.
  • X 1 and X 2 are alkylene groups having 1 to 5 carbon atoms which may independently have a substituent, and are preferably 1 carbon atoms. It is an alkylene group having 3 to 3, and more preferably an alkylene group having 1 or 2 carbon atoms.
  • i and ii each independently represent an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably 1 or 2.
  • R 1 , R 2 , R 3 to R 10 , R 13 to R 20 and X are in the formulas (1-1) and (1-2). The same applies to R 1 , R 2 , R 3 to R 10 , R 13 to R 20 , and X, respectively.
  • the 1% mass reduction pyrolysis temperature is preferably 300 ° C. or higher, more preferably the 1% mass reduction pyrolysis temperature is 320 ° C. or higher, and further preferably 1% mass reduction.
  • the pyrolysis temperature is 330 ° C. or higher, and particularly preferably, the 1% mass reduction pyrolysis temperature is 350 ° C. or higher.
  • the mass reduction rate at 500 ° C. is preferably 40% or less, more preferably 30% or less, still more preferably 25% or less. It is more preferably 20% or less, and particularly preferably 17% or less. That is, the mass retention rate (%) of the thermoplastic resin at 500 ° C., which is the value of 100- "500 ° C. mass reduction rate (%)", is 60% or more. It is preferably 70% or more, more preferably 75% or more, further preferably 80% or more, and particularly preferably 83% or more.
  • the ratio of the total weight (total Si amount) of the silicon atoms based on the total weight of the thermoplastic resin is preferably 0.1 to 20% by mass or 0.1 to 17% by mass. , 1.0 to 15% by mass, more preferably 2.0 to 12% by mass, and 3.0 to 10% by mass (for example, 3.1% by mass or more, or 3.1). (More than mass% and 9.8% by mass or less) is particularly preferable.
  • composition according to the present invention that is, the composition containing the above-mentioned thermoplastic resin and the like will be described in detail.
  • composition of the present invention is the above-mentioned thermoplastic resin, that is, the above-mentioned ⁇ 1.
  • the thermoplastic resin described in the> Thermoplastic resin> column and the polycarbonate resin which does not correspond to the above-mentioned thermoplastic resin are included.
  • the polycarbonate resin that does not correspond to the above-mentioned thermoplastic resin include a polycarbonate resin that completely or substantially does not contain a siloxane structure (constituent unit (A)).
  • the molecular main chain contains a carbonic acid ester bond- [OR-OCO] -unit (R is an aliphatic group, an aromatic group, or an aliphatic group). It is not particularly limited as long as it contains both a group and an aromatic group, and further has a linear structure or a branched structure).
  • the polycarbonate resin that does not correspond to the above-mentioned thermoplastic resin may contain polyester carbonate.
  • the polyester carbonate is not particularly limited as long as it contains a carbonic acid ester bond in the molecular main chain- [OR-OC] -unit (R is as described above).
  • the weight average molecular weight of the polycarbonate resin which does not correspond to the above-mentioned thermoplastic resin, is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and further preferably 15,000 to 15,000. It is 60,000.
  • the composition of the present invention may contain a resin other than the polycarbonate resin, preferably a thermoplastic resin.
  • the type of the thermoplastic resin is not particularly limited, but in addition to the polycarbonate resin and the polyester carbonate resin, an acrylic resin such as polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polyethylene naphthalate ( Examples thereof include various resins such as PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, and aromatic polyamide.
  • PMMA polymethylmethacrylate
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • naphthalate examples thereof include various resins such as PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, and aromatic
  • the ratio of the total weight (total Si amount) of the silicon atoms based on the total weight of the composition is preferably 0.1 to 20% by mass, preferably 0.2 to 15% by mass. It is more preferable, and it is particularly preferable that it is 0.3 to 10% by mass.
  • the ratio of the total Si amount in the composition can be adjusted by the ratio of the siloxane constituent unit to the total constituent units in the above-mentioned polycarbonate resin, or the amount of the resin mixed with the polycarbonate resin and the amount of Si.
  • Q 1 which is a Q value measured under the condition of 280 ° C.
  • Q 2 which is a Q value measured only by the polycarbonate resin contained in the composition under the same conditions.
  • the value is preferably 120% or more (20% or more higher), and the Q 1 value of the entire composition is more preferably 130% or more, more preferably 130% or more, as compared with the Q 2 value of polycarbonate alone.
  • Q 1 which is a Q value measured under the conditions of 280 ° C.
  • Q 1 is preferably 140% or more (40% or more higher) than the value of Q 2 , and the value of Q 1 of the entire composition is more preferably compared with the value of Q 2 of polycarbonate alone. It is 150% or more, more preferably 160% or more, and particularly preferably 170% or more, for example, 180% or more.
  • thermoplastic resin with a high Si content a composition with excellent characteristics can be produced.
  • the composition containing the thermoplastic resin may include a phenol-based compound that may be produced as a by-product of the polymerization reaction, a silane-based compound that remains without the reaction, a carbonate compound, and a diol compound.
  • Phenolic compounds and diphenyl carbonate (DPC) which are impurities, can cause a decrease in strength and generation of odor when formed into a molded product. Therefore, it is preferable that the content thereof is as small as possible. Therefore, the content of the phenolic compound, the silane compound, the carbonate compound and the diol compound may be reduced so as not to be detected, but from the viewpoint of productivity, the content is contained in the composition as long as the effect is not impaired. May be.
  • a predetermined amount of the remaining amount of the monomer for example, 1 to 1000 wt ppm, preferably 10 to 900 ppm, more preferably 20 to 800 ppm of the monomer is contained, so that the monomer at the time of molding is contained.
  • the effect of improving the fluidity can be obtained, and the plasticity can be improved when the resin is melted.
  • the molded product according to the present invention is obtained by molding the above-mentioned thermoplastic resin, a composition containing the thermoplastic resin, or the like.
  • the molding method of the molded body is not particularly limited, and examples of the molded body include an injection molded product, a press molded product, a blow molded product, an extrusion molded product, a vacuum molded product, and a pressure molded product.
  • the optical lens according to the present invention is obtained by molding the thermoplastic resin of the present invention, a composition containing the thermoplastic resin, or the like as a molded body.
  • the thermoplastic resin of the present invention is suitable for optical applications, and the optical lens of the present invention has a refractive index, Abbe number, etc. in a range suitable for a lens.
  • molded product obtained by using the molded product thermoplastic resin other than the lens
  • parts such as electrical and electronic equipment, OA (Office Automation) equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, lighting equipment, etc.
  • OA Office Automation
  • Parts of various household electric appliances housings of electric appliances, containers, covers, storage parts, cases, covers and cases of lighting appliances, and the like.
  • Examples of electrical and electronic devices include personal computers, game machines, television receivers, display devices such as liquid crystal display devices and plasma display devices, printers, copy machines, scanners, fax machines, electronic notebooks and mobile information terminals (PDAs), and electronic devices.
  • Desktop computers electronic dictionaries, cameras, video cameras, mobile phones, battery packs, recording medium drives and readers, mice, ten keys, CD (Compact Disc) players, MD (MiniDisc) players, portable radio / audio players, etc. Can be mentioned.
  • examples of the molded product include an illuminated signboard, a liquid crystal backlight, a lighting display, a traffic sign, a sign board, a screen, an automobile part (vehicle-mounted part) such as a reflector and a meter part, a toy, a decorative item, and the like. ..
  • the thermoplastic resin of the present invention has excellent impact resistance, high fluidity when melted, and can be a molded body having a fine structure, it is suitably used as an electric / electronic part, a mechanical part, and a vehicle part for automobiles. It can be done.
  • Examples of such parts include automobile interior panels, automobile lamp lenses, automobile inner lenses, automobile lens protective covers, automobile light guides, and the like.
  • the method for producing a molded product of the present invention is not particularly limited, and any molding method generally used for resins such as polycarbonate resin can be arbitrarily adopted.
  • any molding method generally used for resins such as polycarbonate resin can be arbitrarily adopted.
  • an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used.
  • Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, etc. can be mentioned.
  • a molding method using a hot runner method can also be used for manufacturing the molded product.
  • a diaryloxysilane compound (Si (CH), which is an example of a diol compound such as hydroquinone (HQ) or 4,4'-biphenyldiol (BP) and a silane compound and has two methyl groups and a phenoxy group.
  • Si (CH) diaryloxysilane compound
  • HQ hydroquinone
  • BP 4,4'-biphenyldiol
  • a thermoplastic resin is obtained as shown by the following formula (A) or (B).
  • alcohols derived from silane compounds for example, allyl alcohols such as phenols (PhOH) represented by the formulas (A) and (B) can be produced as by-products.
  • the polymerization reaction in a state where the mixture of the above-mentioned components is melted, the polymerization reaction is carried out under reduced pressure while removing alcohols as by-products, for example, allyl alcohol such as phenol, alkyl alcohol and the like. ..
  • the oxysilane compound used in the production of the thermoplastic resin can be selected from a diallyloxysilane compound and a dialkoxysilane compound.
  • Diaryloxysilane compounds include dialkyldiaryloxysilanes, diaryldiaryloxysilanes, and monoalkyl monoaryldiaryloxysilanes.
  • the dialkoxysilane compound includes a dialkyldialkoxysilane, a diallyldialkoxysilane, and a monoalkylmonoaryldialkoxysilane. Specifically, these oxysilane compounds are as follows.
  • the oxysilane compound used in the polymerization step is used to form a siloxane structural unit (constituent unit (A)) in the thermoplastic resin, for example, as represented by the above formula (A).
  • the oxysilane compound is not particularly limited as long as it can be formed in the main chain of the thermoplastic resin, but is selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound). Ru.
  • a silane compound containing at least one of the diaryloxysilane compounds described in detail later, at least one of the dialkoxysilane compounds, and at least one of the silicon compounds is used.
  • the 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 the diaryloxysilane compound and silicon may be used in combination.
  • a mixture of compounds, a mixture of a dialkoxysilane compound and a silicon compound, and a mixture of a diallyloxysilane compound and a dialkoxysilane compound may be used.
  • the diaryloxysilane compound will be described.
  • diaryloxysilane compound examples include dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkyl monoaryldiaryloxysilane. That is, in the polymerization step, any one or a plurality of these may be used as the silane compound.
  • Ra and R b are independently selected from an alkyl group and an aryl group, respectively. It is preferable that R a and R b are each independently an alkyl group having a total carbon number of 1 to 20 and an aryl group having a total carbon number of 6 to 30. More preferably, when Ra and R b are alkyl groups which may have a substituent, the total number of carbon atoms is preferably 1 to 10, and the total number of carbon atoms is more preferably 1 to 6. It is preferable that the total number of carbon atoms is 1 or 2. When Ra and R b are aryl groups that may have a substituent, the total number of carbon atoms is preferably 6 to 20, and more preferably 6 to 12 carbon atoms. It is particularly preferable that the total number of carbon atoms is 6 to 8.
  • Examples of the above-mentioned substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth) acrylic oxy group, a glycidyl oxy group, a mercapto group and the like.
  • Preferred specific examples of Ra and R b in the formula (1 ) include a methyl group, a phenyl group, a vinyl group, and a propyl group.
  • the aryloxy group (OAr group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but is a by-product such as phenol (for example). ArOH) is produced. Therefore, the type of aryloxy group is not particularly limited. However, the aryloxy group preferably has a low polarity and a low molecular weight so that by-products in the polymerization step can be removed from the reaction system as easily as possible, and is, for example, a phenoxy group.
  • dialkyldiaryloxysilane examples include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane, and the like
  • diaryldiaryloxysilane examples include diphenyldiphenyloxysilane.
  • monoalkyl monoaryldiaryloxysilane examples include methylphenylphenoxysilane.
  • dialkoxysilane compound examples include dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane. That is, in the polymerization step, any one or a plurality of these may be used as the silane compound.
  • the dialkoxysilane compound is represented by the general formula Si (Ra R b ) (OR C ) 2
  • Ra and R b are independently described in the column of ( A-1) Diaryloxysilane compound. It is selected from the same alkyl and aryl groups as R a and R b .
  • the alkoxy group (OR C group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but is a by-product such as methanol (for example). MeOH) is generated. Therefore, the type of alkoxy group is not particularly limited.
  • the alkoxy group (OR C group) is, for example, a methoxy group so that by-products in the polymerization step can be removed from the reaction system as easily as possible.
  • dialkyldialkoxysilane examples include dimethyldimethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, and the like, and specific examples of the diaryldialkoxysilane include diphenyldimethoxysilane.
  • monoalkyl monoaryldialkoxysilane examples include methylphenyldimethoxysilane.
  • silicon compound (siloxane compound)
  • the silicon compound include a predetermined cyclic siloxane compound and a linear siloxane compound. That is, in the polymerization step, any one of these may be used as the silane compound.
  • (III-1) Cyclic siloxane compound examples include 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 which may have a substituent. It is preferable that R c and R d in the formula (5) are an alkyl group having a total carbon number of 1 to 20 or an aryl group having a total carbon number of 6 to 30, respectively, which may have a substituent.
  • R c and R d are alkyl groups which may have a substituent
  • the total carbon number is preferably 1 to 10, more preferably the total carbon number is 1 to 6, and the total carbon number is 1 to 6. It is particularly preferred that the number is 1 or 2.
  • R c and R d are aryl groups that may have a substituent
  • the total number of carbon atoms is preferably 6 to 20, and more preferably 6 to 12 carbon atoms. It is particularly preferable that the total number of carbon atoms is 6 to 8.
  • R c and R d in the 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 above-mentioned R c group and -OSi (R c R d ) O- structure having an R d group.
  • the -OSI (R cR d ) O-site of such a cyclic siloxane compound is introduced into the polycarbonate copolymer described in detail later.
  • n represents an integer of 3 or more and 30 or less.
  • the value of n in the 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, and particularly preferably 3 or more and 5 or less. Is.
  • the molecular weight of the cyclic siloxane compound represented by the formula (5) is preferably 2,000 or less, more preferably 1,600 or less, further preferably 1,200 or less, and 1,000. The following is particularly preferable.
  • the molecular weight of the cyclic siloxane compound represented by the formula (5) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.
  • (III-2) Linear Siloxane Compounds examples include a linear siloxane compound represented by the following formula (6).
  • Re and R f each independently represent an alkyl group or an aryl group which may have a substituent. It is preferable that Re and R f in the formula (6) are an alkyl group having a total carbon number of 1 to 20 or an aryl group having a total carbon number of 6 to 30, respectively, which may have a substituent.
  • the total carbon number is preferably 1 to 10, more preferably the total carbon number is 1 to 8, and the total carbon number is 1 to 8.
  • the number is 1 or 2.
  • the total number of carbon atoms is preferably 6 to 20, and more preferably 6 to 12 carbon atoms. It is particularly preferable that the total number of carbon atoms is 6 to 8.
  • substituents examples include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth) acrylic oxy group, a glycidyl oxy group, a mercapto group and the like.
  • Preferred specific examples of Re and R f in the 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 above-mentioned Re group and -OSi (R eR f ) O- structure having an R f group.
  • the -OSI (Re R f ) O-site of the linear siloxane compound is introduced into the polycarbonate copolymer, which will be described in detail later.
  • m represents an integer of 2 or more and 10,000 or less.
  • the value of m in the formula (6) is preferably 10 or more and 7,000 or less, more preferably 100 or more and 2,000 or less, and further preferably 200 or more and 500 or less.
  • X may independently have a hydrogen atom, a hydroxyl group, an alkoxy group having a total carbon number of 1 to 10 and a substituent, and may have an oxygen atom or a nitrogen atom.
  • X may independently have a hydrogen atom, a hydroxyl group, an alkoxy group having a total carbon number of 1 to 10 and a substituent, and may have an oxygen atom or a nitrogen atom.
  • alkyl groups having a total carbon number of 1 to 10 may be more preferably a hydroxyl group or an alkyl group having a total carbon number of 1 to 10 which may have a substituent, and more preferably.
  • substituent of X include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth) acrylic oxy group, a glycidyl oxy group, a mercapto group and the like.
  • the molecular weight of the linear siloxane compound represented by the formula (6) is preferably 60,000 or less, more preferably 56,000 or less, still more preferably 50,000 or less, and 45, It is particularly preferably 000 or less.
  • the molecular weight of the linear siloxane compound represented by the 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, and two or more kinds of siloxane compounds may be used. It may be used as a mixture. Further, the siloxane compound of the formula (5) or the formula (6) may be used in combination with the above-mentioned (A) diaryloxysilane compound.
  • the above-mentioned silane compound can be synthesized by a known method, and a commercially available compound may be used.
  • the aromatic diol compound is used to form the main chain of the polycarbonate copolymer as represented by the above formulas (A) and (B) relating to the outline of the polymerization reaction.
  • Examples of the aromatic diol compound used in the polymerization step include the following, in addition to the above-mentioned hydroquinone (HQ) and 4,4'-biphenyldiol (BP).
  • an alicyclic diol compound or the like may be further used.
  • 50 mol% or more of the aromatic diol represented by the above formula (IV) is preferably used as the diol compound, and more preferably 70 mol of the aromatic diol represented by the formula (IV) is used.
  • the above-mentioned oxysilane compound and the above-mentioned diol compound are polymerized using a catalyst under reduced pressure in a molten state while removing the generated aryl alcohol and / or alkyl alcohol.
  • a thermoplastic resin containing the structural unit (A) represented by the above-mentioned general formula (I) can be obtained.
  • (V-1) Alkali metal-based catalyst As the catalyst used in the polymerization step, a catalyst containing a basic compound is preferable.
  • the basic compound catalyst include those containing an alkali metal compound, an alkaline earth metal compound, and the like, and examples of such a compound include an alkali metal compound, an organic acid salt such as an alkaline earth metal compound, and a carbonate. Inorganic salts such as, oxides, hydroxides, hydrides, alkalis and the like can be mentioned.
  • quaternary ammonium hydroxide and salts thereof, amines and the like are used as a basic compound catalyst. In addition, these compounds can be used alone or in combination of a plurality of types.
  • the catalyst more preferably contains an alkali metal carbonate or an alkali metal hydroxide.
  • specific examples of more preferable catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide and the like.
  • the above-mentioned catalyst can be prepared by a known method, and a commercially available catalyst may be used.
  • (V-2) Phosphorus-based catalyst As the catalyst used in the polymerization step, a catalyst containing a phosphorus compound is also preferably used.
  • the phosphorus-based catalyst preferably contains at least a compound represented by the following general formula (8). (Pre 4 ) + (Xc ) -... (8)
  • Re independently represents an alkyl group, an aryl group, or an alkylaryl group, and a plurality of Res may be bonded to each other to form a ring structure, preferably having a carbon number of carbons. It is an aryl group of 6 to 16.
  • Xc is a hydroxyl group, a halogen atom, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BRf 4 (Rf is an independent hydrogen atom, respectively).
  • Rf is an independent hydrogen atom, respectively.
  • An alkyl group, or an aryl group preferably an aryloxy group containing an aryl group having 6 to 16 carbon atoms, a BRf 4 containing an aryl group having 6 to 16 carbon atoms as Rf 4 , and the like.
  • the aryl group having 6 to 16 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 8 carbon atoms.
  • phosphorus-based catalysts include biphenyltriphenylphosphonium hydroxide, biphenyltriphenylphosphoniumtetraphenylborate, biphenyltriphenylphosphonium phenoxide, biphenyltriphenylphosphonium chloride, tetraphenylphosphonium hydroxide, and methoxyphenyltriphenylphosphonium hydroxide.
  • reaction conditions of the polymerization process In the polymerization step, the mixture of the above-mentioned components is melted, and the by-product aryl alcohol or alkyl alcohol is removed under reduced pressure as a melted state. By setting the reaction conditions in this way, the polymerization reaction can proceed efficiently.
  • the reaction pressure it is preferable to gradually reduce the reaction pressure and then adjust the reaction pressure to a predetermined level. That is, in the polymerization step, it is preferable to maintain a normal pressure state without reducing the pressure for a certain period of time, or a state in which the pressure is not reduced so much, and then reduce the pressure in the system to further proceed with the polymerization reaction. Specifically, it is preferable to set the value to 24,000 Pa or more, gradually reduce the value to less than 100 Pa, and proceed with the polymerization reaction under the reduced pressure.
  • the reaction is carried out 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, less than 100 Pa. It is preferable to gradually reduce the pressure to less than 100 Pa.
  • the decompression step of gradually depressurizing the inside of the reaction system to improve the degree of decompression is preferable because alcohol as a by-product can be efficiently removed while suppressing distilling of the raw material. Further, it is preferable to adjust the reaction pressure to less than 100 Pa regardless of the presence or absence of a gradual decrease.
  • the time of the polymerization step is appropriately determined in consideration of the type, pressure, temperature and other conditions of the target polycarbonate copolymer, but for example, the total time required for the polymerization step is within 5 to 10 hours. More specifically, the reaction time in the reaction system before decompression is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after decompression is 1 to 5 hours, preferably 2 to 4 hours. It's time.
  • the temperature in the above-mentioned polymerization reaction is preferably in the range of 150 to 300 ° C. More preferably, the temperature of the polymerization reaction is 180 to 290 ° C, and even more preferably 200 to 280 ° C.
  • the compatibility of each component of the above-mentioned silane compound and aromatic diol compound with each other is good, and a polycarbonate copolymer can be produced without using a solvent in the polymerization step. Therefore, the polymerization process can be simplified.
  • the ratio of the molar amount of the catalyst to the molar amount of the aromatic diol compound is 1.0 ⁇ 10 -7 to 1. It is preferably 0.0 ⁇ 10 -2 (mol / mol: 0.1 to 10000 ⁇ mol / mol, or 1.0 ⁇ 10 -4 to 10 mmol / mol).
  • the molar ratio is more preferably 1.0 ⁇ 10 -7 to 2.0 ⁇ 10 -5 mol / mol (or 0.5 to 20 ⁇ mol / mol).
  • the molar ratio of the aromatic diol compound (diol compound) to the silane compound (oxysilane compound) is, for example, 0.8. It is about 1.3, preferably 0.9 or more and 1.2 or less, or 0.9 or more and 1.25 or less, and more preferably 0.95 or more and 1.2 or less.
  • the molar ratio of the aromatic diol compound (diol compound) to the total number of moles of the diaryl carbonate and the silane compound (oxysilane compound) (that is, (the total number of moles of the diaryl carbonate and the silane compound) / aromatic).
  • the value of the number of moles of the diol compound) is preferably 0.9 or more and 1.2 or less, more preferably 0.95 or more and 1.15 or less.
  • a molecular weight measuring step for measuring the molecular weight of the thermoplastic resin obtained in the polymerization step for example, the weight average molecular weight may be carried out.
  • the method for measuring the molecular weight will be described later.
  • a predetermined target value is set for the molecular weight of the thermoplastic resin produced by the polymerization step, for example, the weight average molecular weight (Mw), and the measured molecular weight value is out of the range of the target value, the target value is particularly high. If it is lower than that, an additional polymerization step of polymerizing the thermoplastic resin again may be carried out.
  • the target value of the molecular weight of the thermoplastic resin include the above-mentioned preferable range of the weight average molecular weight (Mw), for example, 10,000 to 300,000, 10,000 to 200,000, 15,000 to 100, and so on. 000, 20,000 to 80,000, 30,000 to 70,000, 40,000 to 65,000 and the like can be mentioned. Further, from the viewpoint of preventing insufficient polymerization, a target value may be set as only the lower limit of the weight average molecular weight, for example, 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more. 30,000 or more, 35,000 or more, etc. are listed as the target values of the lower limit.
  • Mw weight average molecular weight
  • the time of the additional polymerization step is appropriately determined in consideration of various conditions as in the polymerization step.
  • the time of the additional polymerization step is 20 minutes to 5 hours, 30 minutes to 4 hours, 1 to 3 hours. 1.5 to 2.5 hours.
  • the temperature of the polymerization reaction in the additional polymerization step is preferably in the range of 150 to 300 ° C. More preferably, the temperature of the polymerization reaction is 180 to 290 ° C, and even more preferably 200 to 280 ° C, for example 220 to 260 ° C.
  • the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability after the completion of the polymerization reaction for production.
  • a method of deactivating the catalyst by adding a known acidic substance can be preferably carried out.
  • the acidic substance include esters such as butyl benzoate and aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonic acid.
  • Phosphates such as phosphite, phosphoric acid, phosphonic acid; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, din-propyl phosphite, diphosphate diphosphate
  • Subphosphate esters such as n-butyl, din-hexyl phosphite, dioctyl phosphite, monooctyl phosphite; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphate.
  • 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 diethylphenylphosphonate; triphenylphosphine and bis (diphenylphosphino) Phosphins such as ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium salt of dodecylbenzene sulfonic acid; organic halides such as chloride chloride, benzoyl chloride and p-toluenesulfonic acid chloride.
  • Alkyl sulfate such as dimethyl sulfate
  • organic halides such as benzyl chloride are preferably used.
  • deactivating agents may be used, for example, in an amount of 0.001 to 50 times mol, preferably 0.01 to 30 times mol, based on the amount of the catalyst.
  • Stabilizers may be added to the thermoplastic resin and molded article of the present invention.
  • stabilizers include heat stabilizers and antioxidants.
  • the ratio of the stabilizer added is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and further preferably 0.02 part by mass or more with respect to 100 parts by mass of the thermoplastic resin. Also, it is preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and further preferably 1.0 part by mass or less.
  • the stabilizer may contain only one kind, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • Heat Stabilizer examples include phenol-based, phosphorus-based, and sulfur-based heat stabilizers.
  • phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphite, phosphinic acid, and polyphosphate
  • acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, potassium pyrophosphate, and calcium pyrophosphate
  • phosphoric acid Phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate and the like; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds and the like can be mentioned.
  • the phosphite ester compound (a), phosphite (b) and tetrakis are esterified with phenol and / or phenol in which at least one ester in the molecule has 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.
  • subphosphate ester compound (a) examples include trioctylphosphite, trioctadecylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, triphenylphosphite, and tris (monononylphenyl) phos.
  • organic phosphite compound examples include "ADEKA STAB 1178 (trade name, the same applies hereinafter)", "ADEKA STAB 2112", “ADEKA STAB HP-10” manufactured by Adeka Corporation, and "JP-351” and “JP-360” manufactured by Johoku Chemical Industry Co., Ltd. , "JP-3CP”, “Irgafos 168” manufactured by BASF, and the like.
  • the phosphoric acid ester 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 part by mass or more, more preferably 0.01 part by mass or more, and further preferably 0.03 part by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the amount is more than 1 part, preferably 1 part by mass or less, more preferably 0.7 part by mass or less, and further preferably 0.5 part by mass or less.
  • the heat stabilizer may contain only one kind, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • antioxidants examples include a phenol-based antioxidant, a hindered phenol-based antioxidant, a bisphenol-based antioxidant, a polyphenol-based antioxidant, and the like. Specifically, 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'-butylidenebis- (3-Methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis ⁇ 2- [3- [3-] (3-tert-Butane, 2,6-
  • the phenolic antioxidant examples include BASF's "Irganox 1010” (registered trademark, the same applies hereinafter), “Irganox 1076", Adeka's "Adeka Stub AO-50", “Adeka Stub AO-60” and the like. be able to.
  • the ratio of the antioxidant added is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 1 part by mass with respect to 100 parts by mass of the thermoplastic resin. Hereinafter, it is more preferably 0.5 parts by mass or less.
  • the antioxidant may contain only one type, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the thermoplastic resin and the molded product of the present invention may contain various additives in addition to the above-mentioned secondary components as long as the gist of the present invention is not deviated.
  • the additive include at least one additive selected from a flame retardant, a flame retardant aid, an ultraviolet absorber, a mold release agent and a colorant, and include at least one of the flame retardant and the mold release agent. Is preferable.
  • an antistatic agent, a fluorescent whitening agent, an antifogging agent, a fluidity improving agent, a plasticizer, a dispersant, an antibacterial agent and the like may be added as long as the desired physical properties are not significantly impaired.
  • UV absorbers in addition to inorganic UV 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, and phenyl salicylate compounds.
  • organic ultraviolet absorbers such as compounds.
  • benzotriazole-based and benzophenone-based organic UV absorbers are preferable.
  • specific examples of the benzotriazole compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [2'-hydroxy-3', 5'-bis ( ⁇ , ⁇ -dimethylbenzyl).
  • 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) is preferable.
  • -6- (2N-benzotriazole 2-yl) phenol examples include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, and 2-hydroxy-4-dodecyloxy.
  • Benzophenone 2-hydroxy-4-octadesiloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 4, Examples thereof include 4'-tetrahydroxy-benzophenone.
  • specific examples of the phenyl salicylate-based ultraviolet absorber include phenyl salicylate, 4-tert-butyl-phenyl salicylate and the like.
  • triazine-based ultraviolet absorbers 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4.
  • the hindered amine-based ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the like.
  • the addition ratio of the ultraviolet absorber is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount is within the above range.
  • the thermoplastic resin and the molded body of the present invention may contain an organic metal salt-based flame retardant, a phosphorus-based flame retardant, a silicone-based flame retardant, or the like as flame retardants.
  • the flame retardant that can be used in the present invention include the flame retardant (flame retardant composition) described in paragraphs 805 to 093 of JP-A-2016-183422, and the contents thereof are incorporated in the present specification.
  • Specific examples of the flame retardant (flame retardant composition) include halogen-based flame retardants, organic metal salt-based flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, antimony-based flame retardants, and flame retardant aids.
  • the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids.
  • the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.
  • the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable.
  • Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cellotic acid, melicic acid, tetrariacontanic acid, and montanic acid.
  • Glutamic acid, adipic acid, azelaic acid and the like can be mentioned.
  • the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol the same one as the above-mentioned aliphatic carboxylic acid can be used.
  • 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 preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable.
  • the aliphatic compound also includes an alicyclic compound.
  • the alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. 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 a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monostearate.
  • Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fishertropush wax, ⁇ -olefin oligomer having 3 to 12 carbon atoms and the like.
  • the aliphatic hydrocarbon also includes an alicyclic hydrocarbon.
  • these hydrocarbon compounds may be partially oxidized.
  • paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
  • the number average molecular weight is preferably 200 to 5000.
  • aliphatic hydrocarbons may be a single substance or a mixture of constituents and various molecular weights, and the main component may be within the above range.
  • the polysiloxane-based 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 release agent is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Hereinafter, it is more preferably 1 part by mass or less. Only one type of 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 is within the above range.
  • the colorant may be either a dye or a pigment, and examples thereof include an inorganic pigment, an organic pigment, and an organic dye.
  • inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc flower, petals, 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; chrome acid pigments such as chrome yellow and molybdate orange; ferrussian such as navy blue. Examples include system pigments.
  • organic pigments and organic dyes as colorants, for example, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green (dye or pigment is referred to as a dye pigment, the same applies hereinafter); azo dyes such as nickel azo yellow.
  • Dye pigments thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, quinophthalone-based, etc.
  • titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and pigments are preferable from the viewpoint of thermal stability.
  • the colorant may be master-batched with a polystyrene-based resin, a polycarbonate-based resin, or an acrylic resin for the purpose of improving the handleability at the time of extrusion and the dispersibility in the resin composition. good.
  • the addition ratio of the colorant 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. Only 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 is within the above range.
  • Mw ⁇ (Wi ⁇ Mi) / ⁇ (Wi) (In the above formula, i represents the i-th division point when the molecular weight M is divided, Wi represents the i-th weight, Mi represents the i-th molecular weight, and the molecular weight M is the same elution time of the calibration curve.
  • Tg glass transition temperature
  • a 5 to 12 mg test piece is weighed in a sample container for AI auto sampler (RDC aluminum pan, cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and the upper part of the sample container is placed on the AI auto sampler. Prepared by sealing with a cover. The measurement was performed using a differential scanning calorimeter (DSC) under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard substance in the reference cell. Then, the measurement sample adjusted to 30 ° C. was heated to 280 ° C.
  • DSC differential scanning calorimeter
  • DSC Differential scanning calorimetry
  • Measuring device Differential thermal mass simultaneous measuring device (TG / DTA) (manufactured by Hitachi High-Tech Science, TG / DTA7300)
  • a 5 mg test piece is weighed in a sample container for AI auto sampler (RDC aluminum pan, cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and the upper part of the sample container is covered with an AI auto sampler. Prepared by sealing with.
  • the measurement was performed using a differential scanning calorimeter (DSC) under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard substance in the reference cell. Then, the measurement sample adjusted to 30 ° C. was heated to 280 ° C.
  • DSC differential scanning calorimeter
  • DSC Differential scanning calorimetry
  • the test piece With the 4 mm thick ISO multipurpose test piece fixed to the test piece mounting jig 2, the test piece was crimped so that the strain amount was 0.72% or 0.4%. After 8 to 24 hours, the molded product was released from caulking, the applied chemicals were wiped off, and then the chemical resistance was visually confirmed according to the following criteria. Especially good: No noticeable appearance defects are seen. Good; The above-mentioned poor appearance is observed, but the occurrence rate of slight or defective is less than 50%. Defects: The above-mentioned poor appearance appears, and it is a level that is difficult to use.
  • Example 1-1 ⁇ Corben scale / catalyst: tetraphenylphosphonium phenoxide> Hydroquinone (HQ) 38.54 g (0.35 mol), dimethyldiphenoxysilane 85.42 g (0.35 mol), and tetraphenylphosphonium phenoxide as a catalyst 10 ⁇ mol / mol (catalyst amount is the number of moles relative to hydroquinone) with a stirrer.
  • HQ Hydroquinone
  • dimethyldiphenoxysilane 85.42 g (0.35 mol) tetraphenylphosphonium phenoxide
  • catalyst amount is the number of moles relative to hydroquinone
  • the DSC chart of the thermoplastic resin (SiHQ) obtained in Example 1-1 is shown in FIG.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 130 minutes, and the temperature inside the system was kept at 250 ° C to less than 1 hPa, and the mixture was held for another 90 minutes to obtain a colorless polysiloxane. rice field.
  • the pressure was adjusted to gradually change to less than 27,000 Pa, 20,000 Pa, 16,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa. ..
  • GPC measurement of the obtained polysiloxane showed Mw of 64,261. Further, the Tg of the polysiloxane is 0 ° C.
  • Tg melting point
  • SiHQ SiHQ in Examples (Examples 1-1 to 1-3, 1-5).
  • 1-6 were generally common. That is, in these examples, the Tg of the polysiloxane was about 0 ° C., which was in the range of -1 ° C. to 1 ° C.
  • Example 1-3 ⁇ Bench scale: Repolymerization of once polymerized resin> Hydroquinone 1.349 kg (12.25 mol), dimethyldiphenoxysilane 3.035 kg (12.44 mol), and cesium carbonate 3 ⁇ mol / mol as catalyst (catalytic amount relative to hydroquinone) equipped with a helical ribbon stirrer. The mixture was placed in a 10 L reaction vessel and the inside of the system was replaced with a nitrogen atmosphere. The raw material was heated and melted at 190 ° C and stirred for 20 minutes.
  • the transesterification reaction was carried out while aggregating and removing the phenol flowing out from the reaction system in a cooling tube over 120 minutes, and the temperature in the system was kept at 250 ° C. to less than 1 hPa, and the mixture was kept for another 120 minutes. Then, the inside of the system was returned to normal pressure with nitrogen to obtain a colorless polysiloxane. At the time of depressurization, it will be less than 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, 100 Pa. The pressure was adjusted to change step by step.
  • PC resin manufactured by Mitsubishi Gas Chemical Company, Upilon (registered trademark) E2000
  • Example 1-5) ⁇ Bench scale, long-term heating / catalyst: cesium carbonate> Hydroquinone 2.292 kg (20.81 mol), dimethyldiphenoxysilane 5.151 kg (21.11 mol), and cesium carbonate 3 ⁇ mol / mol as catalyst (catalytic amount relative to hydroquinone) equipped with a helical ribbon stirrer. The mixture was placed in a 10 L reaction vessel and the inside of the system was replaced with a nitrogen atmosphere. The raw material was heated and melted at 190 ° C and stirred for 20 minutes.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 150 minutes, and the temperature in the system was kept at 250 ° C. to less than 1 hPa and kept for another 240 minutes. Then, the inside of the system was returned to normal pressure with nitrogen to obtain a colorless polysiloxane. At the time of decompression, the pressure gradually increases to 43,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. Adjusted to change. GPC measurement of the obtained polysiloxane showed Mw of 39,970.
  • Example 1-6 ⁇ Corben scale, long-term heating / catalyst: sodium hydrogen carbonate)> 500 ml equipped with a stirrer containing 77.08 g (0.700 mol) of hydroquinone, 173.34 g (0.710 mol) of dimethyldiphenoxysilane, and 12 ⁇ mol / mol of sodium hydrogen carbonate as a catalyst (the amount of substance is relative to hydroquinone). It was placed in a four-necked flask and the inside of the system was replaced with a nitrogen atmosphere. The raw material was heated and melted at 190 ° C and stirred for 30 minutes.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 100 minutes, and the temperature inside the system was kept at 240 ° C to less than 1 hPa, and the mixture was kept for 180 minutes to obtain a colorless polysiloxane. rice field.
  • the pressure was adjusted to gradually change to less than 27,000 Pa, 24,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 6,000 Pa, 2,000 Pa, and 100 Pa.
  • GPC measurement of the obtained polysiloxane showed Mw of 66,267.
  • Tetraphenylphosphonium phenoxide 10.0 ⁇ mol / mol (catalyst amount is the number of moles relative to 2,2-bis (4-hydroxyphenyl) propane) was placed in a 10 L reactor equipped with a stirrer, and the inside of the system was placed in a nitrogen atmosphere. Replaced with. The raw material was heated and melted at 190 ° C. and stirred for 40 minutes.
  • the transesterification reaction was carried out while agglomerating and removing the phenol distilled from the reaction system with a cooling tube, and the temperature in the system was set to 260 ° C. and the degree of decompression was set to 1 hPa or less, and further 1 hour and 15 minutes.
  • a polycarbonate copolymer having a colorless and transparent arylene siloxane structure was obtained.
  • the pressure is changed from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, and 100 Pa or less. The pressure was adjusted so as to change.
  • thermoplastic resin having various properties such as impact resistance, fluidity, flame retardancy and chemical resistance can be obtained.
  • the resin obtained by one polymerization is repolymerized (Example 1-3), and the polymerization reaction time is lengthened (Example). 1-5) was useful.
  • the scale is larger than in Examples 1-1, 1-2 and 1-6 performed on the Kolben scale, the molecular weight of the produced thermoplastic resin tends to be difficult to increase, but the bench.
  • thermoplastic resin having a sufficiently high molecular weight was produced by repolymerization and extension of the reaction time.
  • Example 2 As raw materials, 4,4'-biphenyldiol (BP) 61.4 g (0.33 mol), dimethyldiphenoxysilane (DMDPS) 90.28 g (0.37 mol), and cesium carbonate 3 ⁇ mol / mol as catalyst (catalyst amount 4,4' -The reaction was the same as in Example 1-1 except that the number of moles relative to biphenyldiol) was used. The physical characteristics of the obtained resin are shown in Table 3.
  • FIG. 2 shows the relationship between the weight reduction temperature of the thermoplastic resin obtained in Examples 1-1 and 3 to 5 and Comparative Example 1 and Comparative Example 2 (PC) described later, and the weight%. From Table 5 and FIG. 2, etc., in Comparative Example 1, the rate of thermal decomposition increases at 400 ° C or higher, whereas in SiHQBPA (Examples 1-1, 3 to 5), the charging ratio is 400 ° C or higher. It was confirmed that it showed good heat resistance and could hold a weight of about 80% even at 500 ° C. It was also clarified that the weight loss at 400 ° C or higher was alleviated even when the charging ratio (HQ: BPA) was 3: 7. This result suggests that the addition of a small amount of HQ promotes char formation even when the BPA skeleton is abundantly contained.
  • the reaction was carried out in the same manner as in Example 1-1 except that 12 ⁇ mol / mol of sodium hydrogen carbonate (the amount of catalyst was the number of moles relative to the total amount of HQ and BP) was used.
  • the reaction formula is shown below, and the physical characteristics of the obtained resin (SiHQBP) are shown in Tables 6 and 7.
  • the reaction was carried out in the same manner as in Example 1-1 except that 12 ⁇ mol / mol of sodium hydrogen carbonate (the amount of catalyst was the number of moles relative to the total amount of HQ and BPA) was used.
  • the reaction formula is shown below, and the physical characteristics of the obtained resin (SiBPBPA) are shown in Tables 8 and 9.
  • FIG. 4 shows the relationship between the weight reduction temperature of the thermoplastic resins obtained in Examples 2 and 9 and Comparative Examples 1 and 2 and the weight%. From Table 9 and FIG. 4, the heat resistance of Example 2 (SiBP) and Example 9 (SiBPBPA) at high temperatures was significantly improved as compared with Comparative Example 1 (SiBPA) and Comparative Example 2 (PC), and the temperature was 500 ° C. However, it was confirmed that it could hold 90% of the weight.
  • Example 10 DMDPS + HQ + DPC Hydroquinone 15.48 g (0.14 mol), dimethyldiphenoxysilane 24.02 g (0.098 mol), diphenylcarbonate 9.93 g (0.046 mol), and sodium hydrogen carbonate 12 ⁇ mol / mol as catalyst (catalyst amount is relative to hydroquinone) And was placed in a 100 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw material was heated and melted at 190 ° C and stirred for 30 minutes.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 130 minutes, and the temperature inside the system was kept at 220 ° C to less than 1 hPa, and the mixture was held for another 90 minutes to obtain a colorless polysiloxane. rice field.
  • it will be less than 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, 100 Pa.
  • the pressure was adjusted to change step by step.
  • GPC measurement of the obtained polysiloxane showed Mw of 41508.
  • Example 11 DMDPS + BP + DPC 4,4-Dihydroxybiphenyl 26.18 g (0.14 mol), dimethyldiphenoxysilane 24.02 g (0.098 mol), diphenylcarbonate 9.93 g (0.046 mol), and sodium hydrogen carbonate 12 ⁇ mol / mol as catalyst (catalyst amount relative to hydroquinone) The number of moles) was placed in a 100 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw material was heated and melted at 220 ° C and stirred for 30 minutes.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 130 minutes, and the temperature inside the system was kept at 260 ° C. to less than 1 hPa, and the mixture was kept for 90 minutes to obtain a colorless polysiloxane.
  • rice field At the time of depressurization, 70,000 Pa, 53,000 Pa, 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500. The pressure was adjusted to change gradually to less than Pa and 100 Pa. GPC measurement of the obtained polysiloxane showed Mw of 38951.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 130 minutes, and the temperature inside the system was kept at 220 ° C to less than 1 hPa, and the mixture was held for another 90 minutes to obtain a colorless polysiloxane. rice field.
  • it will be less than 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, 100 Pa.
  • the pressure was adjusted to change step by step. GPC measurement of the obtained polysiloxane showed Mw of 71001.
  • the transesterification reaction was carried out while agglomerating and removing the phenol flowing out from the reaction system in a cooling tube over 130 minutes, and the temperature inside the system was kept at 220 ° C to less than 1 hPa, and the mixture was held for another 90 minutes to obtain a colorless polysiloxane.
  • rice field At the time of depressurization, 70,000 Pa, 53,000 Pa, 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500. The pressure was adjusted to change gradually to less than Pa and 100 Pa. GPC measurement of the obtained polysiloxane showed Mw of 40839.

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Families Citing this family (1)

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EP4177291A1 (en) * 2019-03-22 2023-05-10 Mitsubishi Gas Chemical Company, Inc. Methods for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded body

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS396400B1 (https=) * 1961-07-17 1964-05-04
US4026827A (en) * 1970-01-24 1977-05-31 Dynamit Nobel Aktiengesellschaft Preparation of high-molecular weight thermoplastic polyorganosilicic acid esters
JPH0347842A (ja) * 1989-05-18 1991-02-28 General Electric Co <Ge> ビフェノールと有機ケイ素物質のポリマー性反応生成物およびその製法
JPH08502537A (ja) 1992-10-28 1996-03-19 ヘキスト・アクチェンゲゼルシャフト ポリアリーレンシロキサンおよび遊離基重合性モノマーを基礎とする新規ポリマー
WO2001030787A1 (fr) * 1999-10-28 2001-05-03 National Institute Of Advanced Industrial Science And Technology Polymeres contenant du silicium
JP2016183422A (ja) 2014-06-30 2016-10-20 三菱エンジニアリングプラスチックス株式会社 レーザーダイレクトストラクチャリング層形成用組成物、キット、およびメッキ層付樹脂成形品の製造方法
JP2016532733A (ja) * 2013-10-08 2016-10-20 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 反応性押出しによるシロキサン含有ブロックコポリカーボネートの製造
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1133133B (de) * 1958-01-16 1962-07-12 Goldschmidt Ag Th Verfahren zur Herstellung linearer thermoplastischer Polykondensate aus Diorganosilandiolen und aromatischen Dioxyverbindungen
US4172806A (en) * 1978-02-27 1979-10-30 Dow Corning Corporation Endblocked furfuryloxy organosilicon dielectric fluids and electrical devices containing same
EP0857746A4 (en) * 1996-08-21 1999-11-24 Kaneka Corp PROCESS FOR PREPARING SILOXANE COPOLYMERS AND RESIN COMPOSITIONS CONTAINING SILOXANE COPOLYMERS PREPARED ACCORDING TO SAID PROCESS
RU2014145007A (ru) 2012-04-10 2016-05-27 Моментив Перформанс Матириалз Гмбх Способ получения функциональных силоксанов с регулируемой структурой
EP3247742B1 (de) * 2015-01-20 2020-12-16 Covestro Intellectual Property GmbH & Co. KG Flammgeschützte formmassen enthaltend siloxan-haltiges polycarbonat-blockcokondensat

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS396400B1 (https=) * 1961-07-17 1964-05-04
US4026827A (en) * 1970-01-24 1977-05-31 Dynamit Nobel Aktiengesellschaft Preparation of high-molecular weight thermoplastic polyorganosilicic acid esters
JPH0347842A (ja) * 1989-05-18 1991-02-28 General Electric Co <Ge> ビフェノールと有機ケイ素物質のポリマー性反応生成物およびその製法
JPH08502537A (ja) 1992-10-28 1996-03-19 ヘキスト・アクチェンゲゼルシャフト ポリアリーレンシロキサンおよび遊離基重合性モノマーを基礎とする新規ポリマー
WO2001030787A1 (fr) * 1999-10-28 2001-05-03 National Institute Of Advanced Industrial Science And Technology Polymeres contenant du silicium
JP2016532733A (ja) * 2013-10-08 2016-10-20 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 反応性押出しによるシロキサン含有ブロックコポリカーボネートの製造
JP2016183422A (ja) 2014-06-30 2016-10-20 三菱エンジニアリングプラスチックス株式会社 レーザーダイレクトストラクチャリング層形成用組成物、キット、およびメッキ層付樹脂成形品の製造方法
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DUNNAVANT W R, MARKLE R A, STICKNEY P B, BATTELLE, OL ?, CURRY J E, J D: "Synthesis of polyaryloxysilanes by melt-polymerizing dianilino- and diphenoxysilanes with aromatic diols", JOURNAL OF POLYMER SCIENCE, vol. 5, no. 4, 1 January 1967 (1967-01-01), pages 707 - 724, XP055915019 *
JOURNAL OF POLYMER SCIENCE, vol. 18, 1980, pages 3119 - 3127
See also references of EP4219589A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024122532A1 (ja) * 2022-12-06 2024-06-13 三菱瓦斯化学株式会社 熱可塑性樹脂及び熱可塑性樹脂を含む成形体

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