Method for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded body

Abstract

To provide a method for efficiently producing a polycarbonate copolymer which has siloxane constituent units and exhibits excellent impact resistance and high fluidity when molten; a method for efficiently producing a polycarbonate copolymer or a polysiloxane compound, in which by-products having a high environmental load, such as acids, are not produced, and which can be carried out without the use of solvents requiring safety concerns; and a polysiloxane compound.SOLUTION: This method includes a polymerization step for polymerizing a silane-based compound selected from a prescribed diaryloxysilane compound, a prescribed dialkoxysilane compound and a prescribed silicon compound, a carbonate compound and a diol compound such as an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst. The polymerization step is carried out in a molten state under a reduced pressure while removing alcohols derived from the carbonate compound, thereby producing a polycarbonate copolymer with prescribed siloxane constituent units and prescribed polycarbonate constituent units.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polycarbonate copolymer and a polysiloxane compound, and particularly to a method for producing a polycarbonate copolymer having a siloxane structural unit, a polycarbonate copolymer, etc. [Background technology]

[0002] Thermoplastic polycarbonate resin has excellent impact resistance and mechanical properties, and is formed into various molded products using simple, highly productive processing methods such as injection molding. It is used in a wide range of industrial fields, including electrical and electronic equipment, office automation equipment, heavy electrical machinery, precision machinery, and automotive.

[0003] Conventional polycarbonate resins have the drawback of poor fluidity due to their high melt viscosity, which can make injection molding of precision parts or thin objects difficult. For this reason, it has traditionally been necessary to increase the temperature during molding, and molding at high temperatures has led to problems such as a longer molding cycle, higher costs, and deterioration of the polycarbonate resin during molding. Therefore, attempts have been made to improve the fluidity of polycarbonate resins (Patent Document 1, Patent Document 2), but it has not always been possible to achieve sufficiently high fluidity without impairing the inherent properties of polycarbonate resins (such as impact resistance).

[0004] In addition to polycarbonate resins, aromatic polysiloxane polymers, also known as polyarylenesiloxanes, are known as materials for molded articles produced by molding methods such as injection molding (see, for example, Patent Document 3). In recent years, the importance of polysiloxane compounds such as polyarylenesiloxanes has increased, and polyarylenesiloxanes are used, for example, as release layers in photocopying, photoresist materials, plasticizers for polycarbonates, and components of powder surface coating systems.

[0005] Known methods for producing polysiloxane compounds such as polyarylenesiloxanes include a method in which dimethyldichlorosilane is reacted with bisphenol A in a solvent to produce hydrochloric acid (Non-Patent Document 1), and a method in which the reaction is carried out in a solvent to which acetic acid has been added (Patent Document 4).

[0006] Furthermore, polycarbonate resins, polysiloxane compounds, and the like that are particularly suitable for specific applications such as optical applications have not necessarily been realized to date. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-148047 [Patent Document 2] Japanese Patent Application Publication No. 62-297319 [Patent Document 3] Special Publication No. 08-502537 [Patent Document 4] Special Publication No. 2015-512999 [Non-patent literature]

[0008] [Non-Patent Document 1] Journal of Polymer Science, Vol.18, 3119-3127(1980) Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention provides a polycarbonate copolymer having a siloxane structural unit, which has excellent impact resistance and high fluidity when melted, and a method for efficiently producing the polycarbonate copolymer.

[0010] The present invention also provides a safe and efficient method for producing polycarbonate copolymers and polysiloxane compounds having siloxane structural units, such as polyarylenesiloxanes, without generating corrosive substances such as hydrochloric acid or acetic acid, without requiring the use of solvents, and while reducing the environmental impact.

[0011] Furthermore, the present invention provides polycarbonate resins, polysiloxane compounds, etc. that are particularly suitable for specific applications such as optical applications. [Means for solving the problem]

[0012] The present invention provides the following polycarbonate copolymers, which contain siloxane structural units and have excellent impact resistance and high fluidity, and a method for producing the polycarbonate copolymers. The present invention also provides a method for efficiently producing a polycarbonate copolymer or a polysiloxane compound, which does not produce by-products such as acids that have a high environmental impact, and can be carried out without a solvent, particularly without a solvent that requires safety considerations, and also provides a polysiloxane compound, etc.

[0013] [1] In the presence of a transesterification catalyst, a diaryloxysilane compound containing at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane; a dialkoxysilane compound containing at least one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane; a silicon compound containing at least one of a cyclic siloxane compound and a linear siloxane compound; a silane-based compound selected from the group consisting of a carbonate compound; a polymerization step of polymerizing a diol compound including an aromatic diol compound or an alicyclic diol compound, A method for producing a polycarbonate copolymer having siloxane structural units represented by any one of formulas (1-1) to (1-4) and polycarbonate structural units represented by any one of formulas (3-1) to (3-4), while removing alcohol derived from the carbonate compound in a molten state under reduced pressure in a polymerization step. [ka] (In formulas (1-1) to (1-4), R 1 , and R 2 each independently represents 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 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 to 5, Each K1 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In formulas (3-1) to (3-4), R 13 ~R 20 and R 40 ~R 51 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Z3 and Z4 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J2 each independently represents an integer of 0 to 5, Each K2 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, Y is a single bond or a structural formula represented by formula (4), [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R 21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; c and d each independently represent 0 or an integer of 1 to 5000. [2] Z1 to Z4 each independently represent an alkylene group having 1 to 3 carbon atoms which may have a substituent, J1 and J2 each independently represent an integer of 0 to 2, K1 and K2 each independently represent an integer of 0 or more and 2 or less. A method for producing the polycarbonate copolymer described in [1] above. [3] The X is R 11 and R 12 and / or a siloxane structural unit which represents a fluorene ring structure formed by bonding together, and / or 21 and R 22 The method for producing a polycarbonate copolymer according to the above [1] or [2], wherein the polycarbonate copolymer has polycarbonate structural units that represent a fluorene ring structure formed by bonding together.

[0014] [4] In the presence of a transesterification catalyst, a diaryloxysilane compound containing at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane; a dialkoxysilane compound containing at least one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane; a silicon compound containing at least one of a cyclic siloxane compound and a linear siloxane compound; a silane-based compound selected from the group consisting of The method includes a polymerization step of polymerizing a carbonate compound and a diol compound including an aromatic diol compound or an alicyclic diol compound, A method for producing a polycarbonate copolymer having a siloxane structural unit represented by formula (1) and a polycarbonate structural unit represented by formula (3), wherein the polymerization step involves removing alcohol derived from the carbonate compound in a molten state under reduced pressure. [ka] (In formula (1), R 1 , and R 2each independently represents 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 ~R 10 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X is any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In the formula, R 13 ~R 20 Each of the groups independently represents hydrogen, halogen, alkoxy, or a group having a substituent. 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; a group, or an aryl group having 6 to 30 carbon atoms which may have a substituent, Y is any one of the structural formulas represented by formula (4), [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; c and d each independently represent 0 or an integer of 1 to 5000. [5] The method for producing a polycarbonate copolymer according to any one of the above [1] to [4], wherein the transesterification catalyst contains an alkali metal compound and / or an alkaline earth metal. [6] The method for producing a polycarbonate copolymer according to [5] above, wherein the alkali metal compound and / or alkaline earth metal compound includes a carbonate. [7] The method for producing a polycarbonate copolymer according to any one of the above [1] to [6], wherein the weight average molecular weight of the polycarbonate copolymer is 10,000 to 300,000. [8] In the polymerization step, the amount of the transesterification catalyst relative to the diol compound is 1.0 × 10 in terms of molar ratio. -7 ~1.0×10 -2 The method for producing a polycarbonate copolymer according to any one of the above [1] to [7], [9] The method for producing a polycarbonate copolymer according to any one of the above [1] to [8], wherein the reaction temperature in the polymerization step is in the range of 150°C or higher and 300°C or lower.

[10] The method for producing a polycarbonate copolymer according to any one of the above [1] to [9], further comprising a decompression step of gradually reducing the reaction pressure to 400 Pa or less in the polymerization step.

[11] The method for producing a polycarbonate copolymer according to any one of the above [1] to

[10] , wherein in the polymerization step, the carbonate compound and the diol compound are polymerized under a pressure of 400 Pa or less.

[12] The method for producing a polycarbonate copolymer according to any one of the above [1] to

[11] , wherein no solvent is used in the polymerization step.

[13] The method for producing a polycarbonate copolymer according to any one of the above [1] to

[12] , wherein the ratio of the total number of moles of the carbonate compound and the diaryloxysilane compound to the number of moles of the diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

[14] The method for producing a polycarbonate copolymer according to any one of the above [1] to

[13] , wherein the number of moles of the siloxane structural units in the polycarbonate copolymer is 1 to 1,000, and the number of moles of the polycarbonate structural units is 1 to 1,000.

[15] The method for producing a polycarbonate copolymer according to any one of the above [1] to

[14] , wherein the molar ratio of the siloxane structural units to the polycarbonate structural units is 0.01:99.99 to 99.99:0.01.

[16] The Q value of the polycarbonate copolymer measured under conditions of 280 ° C and 160 kgf is 8 (× 10 -2 cm 3 s -1 The method for producing a polycarbonate copolymer according to any one of the above [1] to

[15] , wherein the polycarbonate copolymer is at least 10% by weight.

[0015]

[17] A polycarbonate copolymer having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4), wherein the content of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less is 30% by weight or less. [ka] (In formulas (1-1) to (1-4), R 1 , and R 2 each independently represents 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 ~R 10 and R 3 ~R 33each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 to 5, Each K1 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In formulas (3-1) to (3-4), R 13 ~R 20 and R 40 ~R 51 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Z3 and Z4 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J2 each independently represents an integer of 0 to 5, Each K2 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, Y is a single bond or a structural formula represented by formula (4), [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R 21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; c and d each independently represent 0 or an integer of 1 to 5000.

[18] Z1 to Z4 each independently represent an alkylene group having 1 to 3 carbon atoms which may have a substituent, J1 and J2 each independently represent an integer of 0 to 2, K1 and K2 each independently represent an integer of 0 or more and 2 or less. The polycarbonate copolymer according to

[17] above.

[19] wherein X is R 11 and R 12 and / or a siloxane structural unit which represents a fluorene ring structure formed by bonding together, and / or 21 and R 22 The polycarbonate copolymer according to

[17] or

[18] above, having polycarbonate structural units that represent a fluorene ring structure formed by bonding together.

[0016]

[20] A polycarbonate copolymer having a siloxane structural unit represented by formula (1) and a polycarbonate structural unit represented by formula (3), wherein the proportion of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less calculated from the GPC area ratio is 30% by weight or less. [ka] (In formula (1), R 1 , and R 2 each independently represents 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 ~R 10 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X is any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In the formula, R 13 ~R 20 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Y is any one of the structural formulas represented by formula (4), [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R 21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; c and d each independently represent 0 or an integer of 1 to 5000.

[21] The polycarbonate copolymer according to any one of the above

[17] to

[20] , wherein the number of moles of the siloxane structural units in the polycarbonate copolymer is 1 to 1,000, and the number of moles of the polycarbonate structural units in the polycarbonate copolymer is 1 to 1,000.

[22] The polycarbonate copolymer according to any one of the above

[17] to

[21] , wherein the molar ratio of the siloxane structural units to the polycarbonate structural units is 0.01:99.9 to 99.9:0.01.

[23] The polycarbonate copolymer according to

[22] above, wherein the molar ratio of the siloxane structural units to the polycarbonate structural units is 30.00:70.00 to 99.9:0.01.

[24] The Q value measured under the conditions of 280°C and 160 kgf is 8(×10 -2 cm 3 s -1 ) or more.

[0017]

[25] A polycarbonate copolymer having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4), wherein the total content of cyclic units represented by formulas (5-1) to (5-3) is 4.0 wt% or less. [ka] (In formulas (1-1) to (1-4), R 1 , and R 2 each independently represents 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 ~R 10 and R 3 ~R 33 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 to 5, Each K1 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In formulas (3-1) to (3-4), R13 ~R 20 and R 40 ~R 51 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Z3 and Z4 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J2 each independently represents an integer of 0 to 5, Each K2 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, Y is a single bond or a structural formula represented by formula (4), [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R 21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; c and d each independently represent 0 or an integer of 1 to 5000. [ka] (In formulas (5-1) to (5-3), m and n represent the total number of structural units containing a (—OSi(R1R2)O—) moiety and the total number of structural units containing a (—OC(═O)O—) moiety in each cyclic structure, respectively; (In formula (5-1), m represents an integer of 2 to 10, In formula (5-2), n represents an integer of 2 to 10. In formula (5-3), the total value of m is 1 to 10, and the total value of n is 1 to 10. In formula (5-3), the structural units containing the (-OSi(R1R2)O-) moiety and the structural units containing the (-OC(=O)O-) moiety may be arranged in any manner. In formulas (5-1) to (5-3), R 1 , and R 2 each independently represents 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 ~R 10 and R 13 ~R 20 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5000.

[26] The polycarbonate copolymer according to any one of the above

[17] to

[25] , wherein the total content of cyclic units of the formulae (6-1) and (6-2) is 2.0% by weight or less. [ka] (In formulas (6-1) and (6-2), R 1 , and R 2 each independently represents 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 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, n represents an integer of 2 to 10; X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less.

[27] The polycarbonate copolymer according to any one of the above

[17] to

[26] , which has a 1% mass loss thermal decomposition temperature of 415°C or lower.

[28] A composition comprising the polycarbonate copolymer according to any one of the above

[17] to

[27] and a polycarbonate resin.

[29] The composition according to

[28] above, wherein the total amount of Si in the composition is 0.1 to 20 mass%.

[30] The composition according to any one of

[28] and

[29] above, wherein Q1, the Q value of the composition measured under conditions of 280°C and 160 kgf, is 120% or more of Q2, the Q value of the polycarbonate resin contained in the composition measured under the same conditions.

[31] A molded article obtained by molding the polycarbonate copolymer according to any one of the above

[17] to

[27] .

[32] An optical lens comprising the polycarbonate copolymer according to any one of

[17] to

[27] above.

[33] An optical lens obtained by molding the composition according to any one of the above items

[28] to

[30] .

[0018]

[34] An oxysilane compound including at least one of a diaryloxysilane compound which is any one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, and a dialkoxysilane compound which is any one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane; a polymerization step of polymerizing a diol compound including an aromatic diol compound or an alicyclic diol compound, In the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure using a transesterification catalyst while removing the resulting aryl alcohol and / or alkyl alcohol, and the amount of the transesterification catalyst relative to the diol compound is 0.01 μmol / mol to 16,000 μmol / mol in terms of molar ratio; A method for producing a polysiloxane compound, which produces a poly(arylene / alkylene)siloxane compound having a weight average molecular weight of 10,000 to 300,000 and containing a structural unit represented by any one of the following formulas (1-1') to (1-4'): [ka] (In formulas (1-1') to (1-4'), R 1 , and R 2 each independently represents 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 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 to 5, Each K1 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, m1 to m4 each represent the total number of structural units in each formula, and are natural numbers of 10 or more and 1000 or less; X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less.

[35] Z1 and Z2 each independently represent an alkylene group having 1 to 3 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 or more and 2 or less, K 12 each independently represents an integer of 0 or more and 2 or less, The method for producing the polysiloxane compound according to

[34] above.

[36] wherein X is R 11 and R 12 and / or a siloxane structural unit which represents a fluorene ring structure formed by bonding together, and / or 21 and R 22

[34] or

[35] above, wherein the polysiloxane compound has polycarbonate structural units that represent a fluorene ring structure formed by bonding together.

[0019]

[37] A method for producing a photopolymerizable composition comprising a polymerization step of polymerizing a diaryloxysilane compound containing at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane with an aromatic diol compound, In the polymerization step, the diaryloxysilane compound and the aromatic diol compound are polymerized in a molten state under reduced pressure using a transesterification catalyst while removing aryl alcohol, and the amount of the transesterification catalyst relative to the aromatic diol compound is 0.01 μmol / mol to 16,000 μmol / mol in terms of molar ratio; A method for producing a polysiloxane compound, which comprises producing a polyarylenesiloxane compound having a weight average molecular weight of 10,000 to 300,000 and containing a constituent unit represented by the following formula (1): [ka] (In the formula, R 1 , and R 2 each independently represents 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 ~R 10each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, m represents a natural number between 10 and 1000, X is any one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less.

[38] The method for producing a polysiloxane compound according to any one of the above

[34] to

[37] , wherein the reaction temperature in the polymerization step is in the range of 150°C or higher and 300°C or lower.

[39] The method for producing a polysiloxane compound according to any one of the above

[34] to

[38] , wherein the reaction pressure in the polymerization step is 101,300 Pa or less.

[40] The method for producing a polysiloxane compound according to any one of

[34] to

[39] above, further comprising a decompression step of gradually reducing the reaction pressure to 400 Pa or less in the polymerization step.

[41] The method for producing a polysiloxane compound according to any one of the above

[34] to

[40] , wherein in the polymerization step, the amount of the transesterification catalyst relative to the aromatic diol compound is 0.1 to 100 μmol / mol in terms of molar ratio.

[42] The method for producing a polysiloxane compound according to any one of the above

[34] to

[41] , wherein the transesterification catalyst contains an alkali metal compound and / or an alkaline earth metal compound.

[43] The method for producing a polysiloxane compound according to

[41] above, wherein the alkali metal compound and / or alkaline earth metal compound includes at least one of a carbonate, a hydroxide, an oxide, and an alkoxy compound.

[44] The method for producing a polysiloxane compound according to

[42] above, wherein the alkali metal compound and / or alkaline earth metal compound is a carbonate.

[45] The method for producing a polysiloxane compound according to any one of the above

[34] to

[44] , wherein no solvent is used in the polymerization step.

[46] The method for producing a polysiloxane compound according to any one of the above

[34] to

[45] , wherein the molar ratio of the diaryloxysilane compound to the aromatic diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

[47] The method for producing a polysiloxane compound according to any one of the above

[34] to

[46] , wherein in the polymerization step, the oxysilane compound or the diaryloxysilane compound and the diol compound or the aromatic diol compound are polymerized at a reaction temperature higher than 200°C and / or under reduced pressure.

[0020]

[48] ​​A polysiloxane compound containing a constitutional unit represented by any one of formulas (1-1) to (1-4), having a weight-average molecular weight of 5,000 to 300,000, and having a total content of cyclic units represented by formula (5-4) of 4.0 wt % or less. [ka] (In formulas (1-1) to (1-4), R 1 , and R 2 each independently represents 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 ~R 10 and R 30 ~R 33each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, J1 each independently represents an integer of 0 to 5, Each K1 independently represents an integer of 0 to 5, A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 to 3, X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less. [ka] (In formula (5-4), the structural unit represented by formula (5-4) may be arranged arbitrarily with other structural units, and the total value of m is 2 to 10, R 1 , and R 2 each independently represents 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 ~R 10each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, m represents an integer from 2 to 10; X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5000.

[49] The polysiloxane compound according to the above

[48] , wherein the total content of cyclic compounds of the formulae (6-1) and (6-2) is 4.0% by weight or less. [ka] (In formulas (6-1) and (6-2), R 1 , and R 2 each independently represents 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 ~R 10 and R 30 ~R 33each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent, X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, n represents an integer from 2 to 10; X is a single bond or any one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5000 or less.

[50] The polysiloxane compound according to

[48] or

[49] above, having a 1% mass loss thermal decomposition temperature of 415°C or lower.

[51] A composition comprising a polysiloxane compound produced by the production method according to any one of the above

[34] to

[46] or the polysiloxane compound according to any one of the above

[48] to

[50] , and a polycarbonate resin.

[52] The composition according to

[51] above, wherein the total amount of Si in the composition is 0.1 to 20 mass%.

[53] The composition according to any one of

[51] and

[52] above, wherein Q1, the Q value of the composition measured under conditions of 280°C and 160 kgf, is 120% or more of Q2, the Q value of the polycarbonate resin contained in the composition measured under the same conditions.

[54] A molded article obtained by molding a polysiloxane compound produced by the production method according to any one of the above

[34] to

[46] or a polysiloxane compound according to any one of the above

[48] to

[50] .

[55] An optical lens comprising a polysiloxane compound produced by the production method according to any one of the above

[34] to

[46] or the polysiloxane compound according to any one of the above

[48] to

[50] . [Effects of the Invention]

[0021] The method for producing a polycarbonate copolymer of the present invention makes it possible to produce a polycarbonate copolymer having siloxane structural units that has high fluidity when melted. Furthermore, the present invention also makes it possible to produce a polycarbonate copolymer having such excellent characteristics, a composition containing the polycarbonate copolymer, and a molded article obtained by molding the polycarbonate copolymer.

[0022] Furthermore, the method for producing a polycarbonate copolymer and the method for producing a polyarylene compound of the present invention enable efficient production of target compounds such as polyarylenesiloxanes without producing by-products such as acids that have a high environmental impact and without requiring solvents. The present invention also enables the realization of polyarylene compounds such as polyarylenesiloxanes with excellent properties. DETAILED DESCRIPTION OF THE INVENTION

[0023] [I. Polycarbonate Copolymer] The method for producing the polycarbonate copolymer of the present invention includes a polymerization step of polymerizing at least one silane compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound) in the presence of a transesterification catalyst, a carbonate compound, and an aromatic diol compound, all of which will be described in detail below.

[0024] The above-mentioned polymerization reaction can be schematically illustrated as follows: For example, when a diaryloxysilane compound (Si(CH3)2(OPh)2) having two methyl groups and a phenoxy group, which is an example of a silane compound, is reacted with diphenyl carbonate (PhO-CO-OPh), which is an example of a carbonate compound, and bisphenol A, which is an example of an aromatic diol compound, the following polycarbonate copolymer is obtained. That is, for example, it is a polycarbonate copolymer having a siloxane structural unit produced by the reaction of the following formula (A) and a polycarbonate structural unit produced by the reaction of the following formula (B). In this polymerization reaction, as described below, an alcohol derived from the carbonate compound is generated as a by-product, for example, an aryl alcohol such as phenol (PhOH) when diaryl carbonate is used as the carbonate compound. Therefore, in the polymerization step, the mixture of the above-mentioned components is melted and the polymerization reaction is allowed to proceed under reduced pressure while removing the by-product alcohol, for example, an aryl alcohol such as phenol. [ka] [ka] The method for producing the polycarbonate copolymer according to the present invention will be described in detail below.

[0025] <1. Method for producing polycarbonate copolymer> [(I) Silane-based compounds] The silane compound used in the polymerization step is used to form siloxane structural units in the polycarbonate copolymer, for example, as shown in the above formula (A). The types of silane compounds are described in detail below, such as -OSi(R 1 R 2The compound is not particularly limited as long as it can form a siloxane structural unit containing a )O-moiety in the main chain of the polycarbonate copolymer, and is selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound).

[0026] That is, in the polymerization step, a silane-based compound containing at least one of diaryloxysilane compounds, at least one of dialkoxysilane compounds, and at least one of silicon compounds, which will be described in detail later, is used. As the silane-based compound, a plurality of diaryloxysilane compounds may be used in combination, a plurality of dialkoxysilane compounds may be used in combination, or a plurality of silicon compounds may be used in combination. Also, a mixture of a diaryloxysilane compound and a silicon compound, a mixture of a dialkoxysilane compound and a silicon compound, or a mixture of a diaryloxysilane compound and a dialkoxysilane compound may be used. Diaryloxysilane compounds will be described below.

[0027] (A-1) Diaryloxysilane Compound Examples of diaryloxysilane compounds include dialkyldiaryloxysilanes, diaryldiaryloxysilanes, and monoalkylmonoaryldiaryloxysilanes. In other words, any one or more of these may be used as the silane-based compound in the polymerization step.

[0028] The diaryloxysilane compound is represented by the general formula Si(R a R b )(OAr)2, R a and R b are each independently selected from alkyl groups and aryl groups. a and R b are preferably each independently an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms, which may have a substituent. a and R bWhen the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 6 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R a and R b When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0029] Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (1) a and R b Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0030] As is clear from the above formula (A), the aryloxy group (OAr group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but generates by-products such as phenol (ArOH). Therefore, the type of aryloxy group is not particularly limited. However, in order to make it possible to remove by-products from the reaction system in the polymerization process as easily as possible, it is preferable that the aryloxy group has low polarity and molecular weight, such as a phenoxy group.

[0031] Specific examples of dialkyldiaryloxysilanes include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane, etc., specific examples of diaryldiaryloxysilanes include diphenyldiphenoxysilane, etc., and specific examples of monoalkylmonoaryldiaryloxysilanes include methylphenylphenoxysilane, etc.

[0032] (A-2) Dialkoxysilane Compound Examples of dialkoxysilane compounds include dialkyldialkoxysilanes, diaryldialkoxysilanes, and monoalkylmonoaryldialkoxysilanes. In other words, any one or more of these may be used as the silane-based compound in the polymerization step.

[0033] The dialkoxysilane compound is represented by the general formula Si(R a R b )(OR C )2, R a and R b are each independently the R described in the column for (A-1) diaryloxysilane compound. a and R b The alkyl and aryl groups are the same as those mentioned above. As is clear from the above formula (A), the alkoxy group (OR C The alkoxy group (OR ) is not introduced into the polymer chain of the polycarbonate copolymer, but generates by-products such as methanol (MeOH). Therefore, the type of alkoxy group is not particularly limited. However, in order to remove by-products in the polymerization process from the reaction system as easily as possible, it is preferable to use an alkoxy group (OR ). C The group) is, for example, a methoxy group.

[0034] Specific examples of dialkyldialkoxysilanes include dimethyldimethoxysilane, methylethyldimethoxysilane, and diethyldimethoxysilane, while specific examples of diaryldialkoxysilanes include diphenyldimethoxysilane, and specific examples of monoalkylmonoaryldialkoxysilanes include methylphenyldimethoxysilane.

[0035] (B) Silicon compounds (siloxane compounds) The silicon compound will be described below. Examples of the silicon compound include a specific cyclic siloxane compound and a linear siloxane compound. That is, either of these may be used as the silane compound in the polymerization step.

[0036] (B-1) Cyclic siloxane compound The siloxane compound used in the polymerization step includes a cyclic siloxane compound represented by the following formula (5). [ka] In equation (5), R c and R d R in formula (5) each independently represents an alkyl group, an alkenyl group, or an aryl group, which may have a substituent. c and R d and are preferably an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms, which may have a substituent. R c and R d When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 6 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R c and R d When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0037] Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (5) c and R d Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0038] The cyclic siloxane compound has a siloxane structure, and the siloxane structure is the above-mentioned R c Groups and R d -OSi(R c R dIn the polymerization process, the -OSi(R c R d )O-moieties are introduced into the polycarbonate copolymer, which will be described in detail below.

[0039] In formula (5), n represents an integer of 3 or more and 30 or less. The value of n in formula (5) is preferably 3 or more and 15 or less, more preferably 3 or more and 10 or less, even more preferably 3 or more and 8 or less, and particularly preferably 3 or more and 5 or less.

[0040] The molecular weight of the cyclic siloxane compound represented by formula (5) is preferably 2,000 or less, more preferably 1,600 or less, even more preferably 1,200 or less, and particularly preferably 1,000 or less. The molecular weight of the cyclic siloxane compound represented by formula (5) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.

[0041] (B-2) Linear siloxane compound The siloxane compound used in the polymerization step also includes a linear siloxane compound represented by the following formula (6). [ka] In equation (6), R e and R f R in formula (6) each independently represents an alkyl group or an aryl group which may have a substituent. e and R f and are preferably an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms, which may have a substituent. R e and R f When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 8 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R eand R f When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0042] Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (6) e and R f Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0043] The linear siloxane compound also has a siloxane structure, and the siloxane structure is the above-mentioned R e Groups and R f -OSi(R e R f In the polymerization process, the linear siloxane compound has a -OSi(R e R f )O-moieties are introduced into the polycarbonate copolymer, which will be described in detail below.

[0044] In formula (6), m represents an integer of 2 or more and 10,000 or less. The value of m in formula (6) is preferably 10 or more and 7,000 or less, more preferably 100 or more and 2,000 or less, and even more preferably 200 or more and 500 or less.

[0045] In formula (6), each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms in total which may have a substituent, a hydrocarbon group having 1 to 10 carbon atoms in total which may have a substituent and which may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. Preferably, each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms in total which may have a substituent, or an alkyl group having 1 to 10 carbon atoms in total which may have a substituent and which may have an oxygen atom or a nitrogen atom, more preferably a hydroxyl group or an alkyl group having 1 to 10 carbon atoms in total which may have a substituent, and even more preferably a hydroxyl group or an alkyl group having 1 to 5 carbon atoms in total. Examples of the substituent for X include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group.

[0046] The molecular weight of the linear siloxane compound represented by formula (6) is preferably 60,000 or less, more preferably 56,000 or less, even more preferably 50,000 or less, and particularly preferably 45,000 or less. The molecular weight of the linear siloxane compound represented by formula (6) is, for example, 1,000 or more, preferably 5,000 or more, and more preferably 10,000 or more.

[0047] Of the cyclic siloxane compound of the above formula (5) and the linear siloxane compound of the following formula (6), a single siloxane compound may be used alone, or two or more types of siloxane compounds may be used as a mixture. Furthermore, the siloxane compound of formula (5) or formula (6) may be used in combination with the above diaryloxysilane compound (A). The above-mentioned silane-based compounds can be synthesized by known methods, and commercially available compounds may also be used.

[0048] [(II) Carbonate compounds] As shown in the above formula (B) showing the outline of the polymerization reaction, carbonate compounds are used to introduce carbonyl groups (-CO- groups) of polycarbonate structural units into polycarbonate copolymers. That is, the two -OR groups of a carbonate compound represented by the general formula RO-CO-OR (where each R is independently selected from an aryl group, an alkyl group, and an aralkyl group), such as the two aryloxy groups (ArO- groups) when the carbonate compound is a diaryl carbonate represented by the general formula ArO-CO-OAr, are not introduced into the polymer chain of the polycarbonate copolymer. These -OR groups generate alcohols derived from the carbonate compound as by-products. For example, carbonate compounds (monoaryl carbonates or diaryl carbonates) having aryloxy groups (ArO- groups) generate aryl alcohols (ArOH) as by-products such as phenols.

[0049] Therefore, the types of aryl group, alkyl group, and aralkyl group of the carbonate compound are not particularly limited. However, in order to make it possible to remove by-products in the polymerization step from the reaction system as easily as possible, it is preferable that the -OR group in the above general formula in the carbonate compound is an aryloxy group (or the -R group in the above general formula RO-CO-OR is an aryl group), and further, it is preferable that the polarity and molecular weight of the carbonate compound are low, and the -OR group in the above general formula is, for example, a phenoxy group. For these reasons, in the carbonate compound, it is preferable that either or both of the Ar groups described above are aryl groups having a total of 10 or less carbon atoms, such as a phenyl group, a benzyl group, etc. That is, preferred specific examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-cresyl carbonate, but dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, or monoaryl monoalkyl carbonates may also be used. The carbonate compounds can be synthesized by known methods, and commercially available compounds may also be used.

[0050] [(III-1) Aromatic diol compounds] The aromatic diol compound used in the polymerization step is used to constitute the main chain of the polycarbonate copolymer, as shown in the above formulas (A) and (B) regarding the outline of the polymerization reaction. Therefore, the aromatic diol compound used in the polymerization step is preferably a monomer that can be used as a material for a polycarbonate resin, such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenyl ethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methoxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Phenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-Bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-sulfonyldiphenol, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5. 2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9 -bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- Examples of such fluorenes include 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (BNEF), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, and 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthren-9-yl)-1,1'-binaphthalene. Among these, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), and 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene (BPMEF) are preferred, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF) are more preferred.

[0051] [(III-2) Alicyclic diol compounds] Examples of the alicyclic diol compound used in the polymerization step include the following. That is, isosorbide represented by the following formula (a compound in which, in the above formula (1-3), L1 and L2 are 1, A1 and A2 are oxygen atoms, and J1, K1, J2, and K2 are 0); [ka] Spiroglycol (SPG) represented by the following formula: [ka] Decahydro-1,4:5,8-dimethanonaphthalenediol (D-NDM, where R is hydrogen) represented by the following formula, etc.; [ka] (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, R is hydrogen.) Cyclohexanedimethanol represented by the following formula: [ka] Pentacyclopentadecanedimethanol (PCPMD) represented by the following formula: [ka] Tricyclodecane dimethanol (TCDDM) represented by the following formula: [ka] Adamantane dimethanol, such as 1,3-adamantanedimethanol, represented by the formula: [ka] etc. The main chain of the polycarbonate copolymer preferably contains structural units derived from these alicyclic diols.

[0052] The above-mentioned polycarbonate copolymer has high fluidity and is suitable for forming molded articles, and is suitably used for forming thin sheets, films, and the like, for example.

[0053] [(IV) Transesterification catalyst] The transesterification catalyst used in the polymerization step is preferably a catalyst containing a basic compound. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Examples of such compounds include organic acid salts of alkali metals and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, and alkoxides. Alternatively, quaternary ammonium hydroxides and their salts, amines, etc. are used as basic compound catalysts. These compounds can be used alone or in combination. The transesterification catalyst preferably contains an alkali metal carbonate or an alkali metal hydroxide among the above-mentioned basic compound catalysts. Specific examples of more preferred transesterification catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. The above-mentioned transesterification catalyst can be prepared by a known method, and commercially available catalysts may also be used.

[0054] [(V) Polymerization process] In the polymerization step, at least the above-mentioned (I) silane compound, (II) carbonate compound, and (III) aromatic diol compound are polymerized in the presence of (IV) a transesterification catalyst. In this polymerization reaction, the mixture of the above components is melted, and in the molten state, alcohols derived from the carbonate compound as by-products, such as aryl alcohols, are removed under reduced pressure. By setting the reaction conditions in this way, the polymerization reaction can proceed efficiently.

[0055] In the polymerization step, it is preferable to allow the polymerization reaction to proceed under a pressure of 400 Pa or less. That is, the pressure in the polymerization reaction is preferably within a range of 400 Pa or less. In the polymerization step, it is preferable to maintain the system at normal pressure without reducing the pressure or at a state where the pressure is not significantly reduced for a certain period of time, and then reduce the pressure inside the system to further promote the polymerization reaction. For example, in the polymerization step, it is preferable to gradually reduce the reaction pressure from the initial atmospheric pressure to 400 Pa or less, such as 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. This decompression step, in which the pressure inside the reaction system is reduced stepwise and the degree of decompression is increased halfway through, is preferable because it allows efficient removal of the by-product alcohol while suppressing distillation of the raw materials.

[0056] The time for the polymerization step is determined appropriately taking into consideration the type of the target polycarbonate copolymer, pressure, temperature, etc., but for example, the total time for the polymerization step is within 5 to 10 hours. More specifically, the reaction time before decompression in the reaction system 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.

[0057] In the polymerization step, the temperature in the above-mentioned polymerization reaction is preferably within a range of 150 to 300°C, more preferably 180 to 290°C, and even more preferably 200 to 280°C.

[0058] Furthermore, the silane compound, diaryl carbonate, and aromatic diol compound have good compatibility with each other, and the polycarbonate copolymer can be produced without using a solvent in the polymerization step, thereby simplifying the polymerization step.

[0059] In the polymerization step, the ratio of the molar amount of the transesterification catalyst to the molar amount of the aromatic diol compound (molar ratio: i.e., the value of the molar amount of the transesterification catalyst / the molar amount of the aromatic diol compound) is 1.0 × 10 -7 ~1.0×10 -2 (mol / mol: 0.1 to 10,000 μmol / mol, or 1.0 × 10 -4 The molar ratio is preferably 1.0 × 10 to 10 mmol / mol. -7 ~2.0×10 -5 mol / mol (or 0.5 to 20 μmol / mol).

[0060] In the polymerization step, the molar ratio of the aromatic diol compound to the silane compound (i.e., the value of the number of moles of the silane compound / the number of moles of the aromatic diol compound) is, for example, 0.8 to 1.3, preferably 0.9 or more and 1.25 or less, and more preferably 0.95 or more and 1.2 or less. In addition, in the polymerization step, the molar ratio of the aromatic diol compound to the total number of moles of the diaryl carbonate and the silane compound (i.e., the value of (total number of moles of the diaryl carbonate and the silane compound) / number of moles of the aromatic diol compound) is preferably 0.9 or more and 1.2 or less, and more preferably 0.95 or more and 1.15 or less.

[0061] Next, the polycarbonate copolymer according to the present invention will be described in detail. <2. Polycarbonate copolymer> [(I) Constitutional Unit] The polycarbonate copolymer produced by the process of the present invention is a polymer having siloxane structural units as described above, and specific examples thereof include the following. That is, the polycarbonate copolymer is a polymer having at least a siloxane structural unit represented by any one of the following formulas (1-1) to (1-4) and a polycarbonate structural unit, the details of which will be described later. [ka] R in formulas (1-1) to (1-4) 1 and R 2 The siloxane structure containing the above is introduced from the diaryloxysilane compound, dialkyldialkoxysilane, or silicon compound (siloxane compound).

[0062] In formulas (1-1) to (1-4), R 1 and R 2 each independently represents 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 1 and R 2 When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R 1 and R 2 When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0063] In formulas (1-1) and (1-2), R 3 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent. R 3 ~R 10 and R 30 ~R 33When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. R 3 ~R 10 and R 30 ~R 33 When the alkyl group is an alkenyl group which may have a substituent, it preferably has a total of 2 to 10 carbon atoms, more preferably has a total of 2 to 6 carbon atoms, and particularly preferably has a total of 2 to 4 carbon atoms. Also, R 3 ~R 10 and R 30 ~R 33 When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0064] In formulas (1-1) to (1-3), Z1 and Z2 are each independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In formulas (1-1) to (1-3), J1 and K1 each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, for example, 1 or 2. In formula (1-3), A1 and A2 each independently represent -O- or -CH-; L1 and L2 each independently represent an integer of 0 or more and 3 or less, and L1 and L2 are preferably 1 or 2. In formulas (1-1) and (1-2), each X is independently a single bond or one of the structural formulas represented by the following formula (2). [ka] In formula (2), R 11 , and R 12each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5,000 or less. R 11 , and R 12 are preferably each independently hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent. In formula (2), a and b are each independently 0 or an integer of 1 or more and 5000 or less, and a and b are preferably integers of 1000 or less, more preferably integers of 500 or less, and even more preferably integers of 100 or less. In the siloxane structural unit, X is R 11 and R 12 are preferably bonded to each other to form a fluorene ring structure.

[0065] The siloxane constitutional unit preferably contains at least one represented by the following formula (1). [ka]

[0066] R in Equation (1) 1 and R 2 The siloxane structure containing the above is introduced from the diaryloxysilane compound, dialkoxysilane compound, or silicon compound (siloxane compound). In formula (1), R 1 and R 2 R in formula (1) each independently represents an alkyl group, an alkenyl group, or an aryl group, which may have a substituent. 1 and R 2are each an alkyl group having a total of 1 to 20 carbon atoms, or an aryl group having a total of 6 to 30 carbon atoms, which may have a substituent. R 1 and R 2 Regarding the preferred options, R in the above formulas (1-1) to (1-4) 1 and R 2 is the same as:

[0067] The above-mentioned R 1 and R 2 Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (1) 1 and R 2 Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0068] In formula (1), R 3 ~R 10 Regarding the preferred options, R in the above formulas (1-1) to (1-4) 3 ~R 10 is the same as: The above-mentioned R 3 ~R 10 Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group.

[0069] In formula (1), X is the same as X in formulas (1-1) and (1-2) above.

[0070] The polycarbonate structural unit of the polycarbonate copolymer is represented by any one of the following formulas (3-1) to (3-4). [ka]

[0071] (3-1)~(3-2) Medium, R 13 ~R 20 and R40 ~R 51 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent. R 13 ~R 20 and R 40 ~R 51 When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. R 13 ~R 20 and R 40 ~R 51 When the alkyl group is an alkenyl group which may have a substituent, it preferably has a total of 2 to 10 carbon atoms, more preferably has a total of 2 to 6 carbon atoms, and particularly preferably has a total of 2 to 4 carbon atoms. Also, R 13 ~R 20 and R 40 ~R 51 When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0072] In formulas (3-1) to (3-3), Z3 and Z4 are each independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In formulas (3-1) to (3-3), J2 and K2 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. In formula (3-3), A1 and A2 each independently represent -O- or -CH-. L1 and L2 each independently represent an integer of 0 or more and 3 or less, and L1 and L2 are preferably 0 or more and 2 or less. In the formulas (3-1) and (3-2), each Y is independently a single bond or any one of the structural formulas represented by formula (4). [ka] (In the formula, R 21 , and R 22 each independently represents hydrogen, halogen, 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, or R 21 and R 22 are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms which may have a substituent, and c and d each independently represent 0 or an integer of 1 to 5,000. R 21 , and R 22 are preferably each independently hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent. In formula (4), c and d are each independently 0 or an integer of 1 or more and 5000 or less, and c and d are preferably integers of 1000 or less, more preferably integers of 500 or less, and even more preferably integers of 100 or less. In addition, in the polycarbonate structural unit, Y is R 11 and R 12 are preferably bonded to each other to form a fluorene ring structure.

[0073] The polycarbonate structural unit preferably contains at least one represented by the following formula (3). [ka]

[0074] In equation (3), R 13 ~R 20 Regarding the preferred options, R in the above formulas (3-1) to (3-2) 3 ~R 10 is the same as: The above-mentioned R 13~R 20 Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group.

[0075] In the formula (3), Y is the same as Y in the above formulas (3-1) and (3-2).

[0076] [(II) Properties of Polycarbonate Copolymer] The weight average molecular weight of the polycarbonate copolymer is preferably 10,000 to 300,000, more preferably 10,000 to 200,000, even more preferably 10,000 to 100,000, for example, more preferably 20,000 to 80,000, even more preferably 30,000 to 70,000, and particularly preferably 40,000 to 65,000.

[0077] In the polycarbonate copolymer, the number of moles of siloxane constituent units is preferably 1 to 1000. The number of moles of polycarbonate constituent units is preferably 1 to 1000. These numbers of moles are the number of constituent units contained in one molecule of the polycarbonate copolymer, and are more preferably 10 to 800, and even more preferably 100 to 600, respectively.

[0078] In the polycarbonate copolymer, the proportion of the siloxane structural units in the total number of moles of the siloxane structural units and the polycarbonate structural units is preferably 2.0% or more and 90% or less. The proportion of the siloxane structural units is more preferably 3.0% or more, for example, more preferably more than 3.1% and 90% or less, even more preferably 5% or more and 90% or less, and particularly preferably 8% or more and 90% or less. Furthermore, when the polycarbonate copolymer is not used alone but is used as a composition mixed with other resins, it may be advantageous to significantly increase the proportion of the above-mentioned siloxane structural units. For example, a polycarbonate copolymer having a high Si content and a proportion of the above-mentioned siloxane structural units of 30% or more, 50% or more, or 70% or more can be mixed with a polymer that does not contain Si or siloxane structural units, as will be described in detail below, to achieve a resin with excellent performance, for example, high impact resistance and fluidity. Furthermore, when an application in which the proportion of the siloxane structural units is increased is preferred, the upper limit of the proportion of the above-mentioned siloxane structural units is not limited to 90%, and may be, for example, 92%, 95%, 98%, etc.

[0079] In the polycarbonate copolymer, the molar ratio of siloxane structural units to polycarbonate structural units (i.e., the ratio of the number of moles of siloxane structural units to the number of moles of polycarbonate structural units) is preferably 0.01:99.99 to 99.99:0.01. The molar ratio is more preferably 30:70 to 99.9:0.01, but may be other ranges, such as 1:99 to 99:1, 10:90 to 90:10, etc.

[0080] For polycarbonate copolymers, the Q value (melt flow volume per unit time measured at 280°C and a load of 160 kg, × 10 -2 cm 3 s -1 ) is 8(×10 -2 cm 3 s -1 ) or more. The Q value is more preferably 20(×10 -2 cm 3 s -1 ) or more, and more preferably 40 (× 10 -2 cm 3 s -1 ) or more, and particularly preferably 60 (× 10 -2 cm 3 s -1 )That's all.

[0081] The polycarbonate copolymer has a glass transition temperature (Tg) according to JIS K 7121 of, for example, 40 to 200°C, preferably 45 to 180°C, and more preferably 50 to 160°C.

[0082] In the above-mentioned polycarbonate copolymer, i.e., a polycarbonate copolymer having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4), the content of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less is preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, more preferably 5.0% by weight or less, particularly preferably 1.5% by weight or less, and even more preferably less than 1.0% by weight. Polycarbonate copolymers containing a large amount of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less tend to contaminate the mold with trace amounts of deposits (mold deposits) at a relatively early stage when injection molding or the like is performed continuously to produce disks or complex, thin-walled products. In this regard, if the amount of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less in the polycarbonate copolymer is less than 1.5% by mass, mold contamination can be effectively prevented. Furthermore, the lower limit of the content of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less in the polycarbonate copolymer is not particularly important, but is about 0.7% by weight. However, even if the polycarbonate copolymer contains 0.001%, 0.01%, or 0.1% by weight or more of these low-molecular-weight compounds, the properties of the polycarbonate copolymer, particularly when used for optical applications, are not affected, and the effect of improving fluidity has also been confirmed. Therefore, the lower limit of the content of low-molecular-weight compounds having a weight-average molecular weight of 1,000 or less in the polycarbonate copolymer may be 0.001%, 0.01%, or 0.1% by weight.

[0083] The content of the above-mentioned low-molecular-weight compounds in the polycarbonate copolymer is a value calculated from the ratio of the peak areas of each component obtained by GPC analysis to sum up the contents of several types of low-molecular-weight compounds that are impurities, as will be described in detail later in the Examples. That is, as will be described in detail later, the proportion of low-molecular-weight compounds having a molecular weight of 1,000 or less in the polycarbonate copolymer is a value calculated from the ratio of the area from 20.5 min to 21.5 min of the retention time to the area from 0 min to 21.5 min under specified GPC analysis conditions.

[0084] In the above-mentioned polycarbonate copolymer, i.e., a polycarbonate copolymer having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4), the total content of cyclic units represented by the following formulas (5-1) to (5-3) is preferably 4.0 wt % or less, more preferably 3.0 wt % or less, even more preferably 2.0 wt % or less, and particularly preferably 1.0 wt % or less, based on the total weight of the polycarbonate copolymer. If the content of these cyclic dimers is within the above range, it can be said that there will be no problem in the properties of the polycarbonate copolymer, particularly when it is used for optical purposes. [ka] In formulas (5-1) to (5-3), m and n represent the total number of structural units containing a (-OSi(R1R2)O-) moiety and the total number of structural units containing a (-OC(=O)O-) moiety in each cyclic compound. That is, when a cyclic compound of formula (5-1) contains a structural unit other than a structural unit containing a (-OSi(R1R2)O-) moiety, or when a cyclic compound of formula (5-2) contains a structural unit other than a structural unit containing a (-OC(=O)O-) moiety, m and n each represent the total number of structural units shown in the formula in the cyclic compound. In particular, formula (5-3) includes a mixture of structural units containing a (-OSi(R1R2)O-) moiety and structural units containing a (-OC(=O)O-) moiety, for example, a cyclic compound in which these are arranged alternately. In this case, m and n each represent the total number of structural units shown in the formula in the cyclic compound. In formula (5-1), m represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2. In formula (5-2), n represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2. In formula (5-3), the total value of m is 1 to 10, and the total value of n is 1 to 10. Each of m and n is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. In formula (5-3), as mentioned above, in the cyclic compound of formula (5-3), the structural unit containing the (—OSi(R1R2)O—) moiety and the structural unit containing the (—OC(═O)O—) moiety may be arranged in any manner. In formulas (5-1) to (5-3), X1 and X2 each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, 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. In addition, in formulas (5-1) to (5-3), R 1 , R 2 , R 3~R 10 , R 13 ~R 20 and X is R in formulas (1-1) and (1-2). 1 , R 2 , R 3 ~R 10 , R 13 ~R 20 and X, respectively.

[0085] Specific examples of the compounds of formulae (5-1) to (5-3) include cyclic compounds of the following formulae (5-1') to (5-3'). [ka] In formula (5-1'), m=2 or 3, preferably m=2; in formula (5-2'), n=2 or 3, preferably n=2; and in formula (5-3'), m=any of 1 to 3, n=any of 1 to 3, preferably 1 or 2 for each, more preferably 1 for each.

[0086] The polycarbonate copolymer may also contain a total content of cyclic compounds represented by the following formulae (6-1) and (6-2). These cyclic compounds are considered to be cyclic dimers produced as a side reaction of the polymerization reaction for producing the polycarbonate copolymer. The total content of these cyclic dimers in the polycarbonate copolymer is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, even more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less, based on the total weight of the polycarbonate copolymer. [ka] In formulas (6-1) and (6-2), R 1 , R 2 , R 3 ~R 10 , R 30 ~R 33 and X are the same as those in formulas (1-1) and (1-2). In formulas (6-1) and (6-2), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms, which may have a substituent. 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. n represents an integer of 2 to 10, preferably an integer of 2 to 5, more preferably 2 or 3, for example, 2.

[0087] The lower limit of the total content of the cyclic dimers represented by formulas (6-1) and (6-2) contained in the polycarbonate copolymer is not particularly limited, and may be, for example, 0.001% by weight, 0.01% by weight, or 0.1% by weight. The presence of a small amount of the cyclic dimer can contribute to improving the flowability of the polycarbonate copolymer during molding.

[0088] Specific examples of the compounds of formula (6-1) and (6-2) include cyclic compounds of the following formulas (6-1') and (6-2'). [ka] In addition, in formulas (6-1') and (6-2'), R 1 and R 2 , R 3 ~R 10 and R 30 ~R 33 , Z1 and Z2, J1, K1 and X are as described above.

[0089] In the polycarbonate copolymer, the 1% mass loss thermal decomposition temperature is preferably 415°C or lower, more preferably 400°C or lower, even more preferably 385°C or lower, and particularly preferably 370°C or lower.

[0090] In the polycarbonate copolymer, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the polycarbonate copolymer is preferably 0.1 to 20 mass%, more preferably 1.0 to 15 mass%, even more preferably 2.0 to 12 mass%, and particularly preferably 3.0 to 10 mass% (for example, 3.1 mass% or more, or more than 3.1 mass% and 9.8 mass% or less).

[0091] Next, the composition according to the present invention, that is, the composition containing the above-mentioned polycarbonate copolymer and the like, will be described in detail.

[0092] <3. Composition> The composition of the present invention contains the above-mentioned polycarbonate copolymer and a polycarbonate resin that does not fall under the category of the above-mentioned polycarbonate copolymer. Examples of the polycarbonate resin that does not fall under the category of the above-mentioned polycarbonate copolymer include polycarbonate resins that are completely or substantially free of siloxane structures.

[0093] The type of polycarbonate resin that does not fall under the above-mentioned polycarbonate copolymer is not particularly limited as long as it contains an -[OR-OCO]- unit containing a carbonate bond in the molecular main chain (where R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). Furthermore, the polycarbonate resin that does not fall under the above-mentioned polycarbonate copolymer may contain polyester carbonate. Similarly, the polyester carbonate is not particularly limited as long as it contains an -[OR-OC]- unit (where R is as described above) containing a carbonate bond in the molecular main chain.

[0094] The weight average molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.

[0095] The composition of the present invention may contain a resin other than a polycarbonate resin, preferably a thermoplastic resin. The type of thermoplastic resin is not particularly limited, but examples thereof include polycarbonate resin, polyester carbonate resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide.

[0096] In the composition, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the composition is preferably 0.1 to 20 mass%, more preferably 0.2 to 15 mass%, and particularly preferably 0.3 to 10 mass%. The proportion of the total Si content in the composition can be adjusted by the proportion of siloxane constituent units to all constituent units in the above-mentioned polycarbonate resin, or by the amount of resin or Si content mixed with the polycarbonate resin. For example, Q1, which is the Q value of a composition containing a polycarbonate copolymer measured under conditions of 280°C and 160 kgf, is preferably 120% or more (20% or more higher) than Q2, which is the Q value of only the polycarbonate resin contained in the composition measured under the same conditions. The Q1 value of the entire composition is more preferably 130% or more, even more preferably 140% or more, and particularly preferably 150% or more, for example 160% or more, of the Q2 value of only the polycarbonate. Furthermore, for example, in the case of a composition containing 5% by mass of a polycarbonate copolymer, Q1, which is the Q value measured under conditions of 280°C and 160 kgf, is preferably 140% or more (40% or more higher) than Q2, which is the Q value measured under the same conditions for only the polycarbonate resin contained in the composition, and the Q1 value of the entire composition is more preferably 150% or more, even more preferably 160% or more, and particularly preferably 170% or more, for example 180% or more, of the Q2 value for only the polycarbonate.

[0097] A composition with excellent characteristics can be produced by using a polycarbonate copolymer with a high Si content. By mixing a polycarbonate copolymer having a Si content of, for example, 0.1 mass % or more with a resin that is substantially free of siloxane structural units, preferably a polycarbonate resin, the resulting composition can have both excellent impact resistance and flowability.

[0098] Compositions containing polycarbonate copolymers may contain phenolic compounds that may be produced as by-products of the polymerization reaction, as well as unreacted silane compounds, carbonate compounds, and diol compounds. The impurities phenolic compounds and DPC can cause a decrease in strength and odor when molded into a molded article, so their content is preferably as low as possible. Therefore, the content of phenolic compounds, silane compounds, carbonate compounds, and diol compounds may be reduced to an undetectable level, but from the viewpoint of productivity, they may be contained in the composition within a range that does not impair the effect. Furthermore, by containing a predetermined amount of residual monomer, for example, 1 to 1,000 ppm by weight, preferably 10 to 900 ppm, and more preferably 20 to 800 ppm, based on the total weight of the composition, the effect of improving fluidity during molding can be obtained, and the plasticity of the resin when melted can be improved.

[0099] Next, the molded article according to the present invention containing a polycarbonate copolymer will be described. <4. Molded body> The molded article according to the present invention is obtained by molding the above-mentioned polycarbonate copolymer or a composition containing the polycarbonate copolymer, etc. The molding method for the molded article is not particularly limited, and examples of the molded article include injection molded articles, press molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and pressure molded articles.

[0100] Furthermore, the optical lens according to the present invention is a molded article obtained by molding the polycarbonate copolymer of the present invention or a composition containing the polycarbonate copolymer, etc. The polycarbonate copolymer of the present invention is suitable for optical applications, and the optical lens of the present invention has a refractive index, Abbe number, etc. within ranges suitable for a lens.

[0101] [II. Polysiloxane Compounds] The method for producing a polysiloxane compound such as polyarylenesiloxane in the present invention includes a polymerization step of polymerizing an oxysilane compound, such as a predetermined diaryloxysilane compound, with a diol compound, such as an aromatic diol compound, in the presence of a transesterification catalyst, as will be described in detail below. The method for producing a polysiloxane compound will be described below. In addition, in the method for producing a polysiloxane compound, the raw materials, reaction conditions, etc. described for the above-mentioned polycarbonate copolymer can also be used, and in the method for producing the above-mentioned polycarbonate copolymer, the raw materials, reaction conditions, etc. described for the following method for producing a polysiloxane compound can also be used.

[0102] The above-mentioned polymerization reaction can be schematically illustrated as follows: For example, when a diphenoxysilane compound (Si(CH)(OPh)), which is an example of a diaryloxysilane compound and has two methyl groups and a phenoxy group, is reacted with bisphenol A, which is an example of an aromatic diol compound, the following polyarylenesiloxane compound is obtained. That is, a polyarylenesiloxane compound having a siloxane structure formed by the reaction of the following formula (A) is produced. In this polymerization reaction, aryl alcohols such as phenol (PhOH) are produced as by-products, as described below. Therefore, in the polymerization step, the mixture of the above-mentioned components is melted and the polymerization reaction is allowed to proceed under reduced pressure while removing the aryl alcohols such as phenol as by-products. [ka] The method for producing a polysiloxane compound according to the present invention will be described in detail below. The polysiloxane compound includes polyarylenesiloxane compounds, polyalkylenesiloxane compounds, and mixtures thereof, as well as compounds containing both a diaryloxysilane compound-derived structural unit and a dialkoxysilane compound-derived structural unit in the polymer chain, as will be described in detail below.

[0103] <1. Method for producing polysiloxane compound> [(I) Oxysilane compound] Examples of oxysilane compounds used in the production of polysiloxane compounds include diaryloxysilane compounds and dialkoxysilane compounds.

[0104] (A-1) Diaryloxysilane Compound The diaryloxysilane compound used in the polymerization step is used to form siloxane constituent units in the polyarylenesiloxane compound, for example, as shown in the above formula (A). Examples of diaryloxysilane compounds include dialkyldiaryloxysilanes, diaryldiaryloxysilanes, and monoalkylmonoaryldiaryloxysilanes. In other words, any one or more of these may be used as the silane-based compound in the polymerization step.

[0105] The diaryloxysilane compound is represented by the general formula Si(R a R b )(OAr)2, R a and R b are each independently selected from alkyl groups and aryl groups. a and R b are preferably each independently either an alkyl group having a total of 1 to 20 carbon atoms, which may have a substituent, or an aryl group having a total of 6 to 30 carbon atoms. a and R bWhen the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 6 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R a and R b When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0106] Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in Equation (1) a and R b Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0107] As is clear from the above formula (A), the aryloxy group (OAr group) of the diaryloxysilane compound is not introduced into the polymer chain of the polyarylenesiloxane compound, but generates by-products such as phenol (ArOH). Therefore, the type of aryloxy group is not particularly limited. However, in order to make it possible to remove by-products from the reaction system in the polymerization process as easily as possible, it is preferable that the aryloxy group has low polarity and molecular weight, such as a phenoxy group.

[0108] Specific examples of dialkyldiaryloxysilanes include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane, etc., specific examples of diaryldiaryloxysilanes include diphenyldiphenoxysilane, etc., and specific examples of monoalkylmonoaryldiaryloxysilanes include methylphenylphenoxysilane, etc. These diaryloxysilane compounds can be synthesized by known methods, and commercially available products may also be used.

[0109] (A-2) Dialkoxysilane Compound Examples of dialkoxysilane compounds include dialkyldialkoxysilanes, diaryldialkoxysilanes, and monoalkylmonoaryldialkoxysilanes. In other words, any one or more of these may be used as the silane-based compound in the polymerization step.

[0110] The dialkoxysilane compound is represented by the general formula Si(R a R b )(OR C )2, R a and R b are each independently the R described in the column for (A-1) diaryloxysilane compound. a and R b The alkyl and aryl groups are the same as those mentioned above. As is clear from the above formula (A), the alkoxy group (OR C The alkoxy group (OR ) is not introduced into the polymer chain of the polycarbonate copolymer, but generates by-products such as methanol (MeOH). Therefore, the type of alkoxy group is not particularly limited. However, in order to remove by-products in the polymerization process from the reaction system as easily as possible, it is preferable to use an alkoxy group (OR ). C The group) is, for example, a methoxy group.

[0111] Specific examples of dialkyldialkoxysilanes include dimethyldimethoxysilane, methylethyldimethoxysilane, and diethyldimethoxysilane, while specific examples of diaryldialkoxysilanes include diphenyldimethoxysilane, and specific examples of monoalkylmonoaryldialkoxysilanes include methylphenyldimethoxysilane.

[0112] [(II) Diol Compound] Examples of the diol compound used in producing the polysiloxane compound include aromatic diol compounds and alicyclic diol compounds. As the diol compound, a mixture of an aromatic diol compound and an alicyclic diol compound may be used.

[0113] (A-1) Aromatic diol compound The aromatic diol compound used in the polymerization step is used to constitute the main chain of a polysiloxane compound such as a polyarylenesiloxane compound, as shown in the above formula (A) which outlines the polymerization reaction. Therefore, the aromatic diol compound used in the polymerization step is preferably a monomer that can be used as a material for a polycarbonate resin, such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenyl ethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methoxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Phenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene, 9,Examples of suitable hydroxyphenyl compounds include 9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-sulfonyldiphenol, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane. In addition, the aromatic diol compounds described in the section [(III-1) Aromatic diol compounds] above regarding the polycarbonate copolymer can also be used in the polymerization step for producing the polysiloxane compound.

[0114] (A-2) Alicyclic diol compound The alicyclic diol compound used in the polymerization step is also used to constitute the main chain of the polysiloxane compound. Specific examples of the alicyclic diol compound include spiroglycol, cyclohexanedimethanol, PCPDM, and TCDDM. In addition, the alicyclic diol compounds described in the section [(III-2) Alicyclic diol compounds] above regarding the polycarbonate copolymer can also be used in the polymerization step for producing the polysiloxane compound.

[0115] [(III) Transesterification catalyst] The transesterification catalyst used in the polymerization step is preferably a catalyst containing a basic compound. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Examples of such compounds include organic acid salts of alkali metals and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, and alkoxides. Alternatively, quaternary ammonium hydroxides and their salts, amines, etc. may be used as basic compound catalysts. These compounds may be used alone or in combination. The transesterification catalyst preferably contains an alkali metal carbonate or an alkali metal hydroxide among the above-mentioned basic compound catalysts. Specific examples of more preferred transesterification catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. The transesterification catalyst can be prepared by a known method, and commercially available catalysts may also be used.

[0116] [(IV) Polymerization process] In the polymerization step, at least (I) a dioxysilane compound such as a diaryloxysilane compound and (II) a diol compound such as an aromatic diol compound are polymerized in the presence of (III) a transesterification catalyst. In this polymerization reaction, the mixture of the above components is melted, and the by-product aryl alcohol and / or alkyl alcohol is removed under reduced pressure in the molten state. By setting the reaction conditions in this way, the polymerization reaction can proceed efficiently.

[0117] In the polymerization step, the pressure in the polymerization reaction is preferably in the range of 101,300 Pa or less, more preferably 27,000 Pa or less, and even more preferably 400 Pa or less. In the polymerization step, it is preferable to maintain normal pressure or a state where the pressure is not significantly reduced for a certain period of time, and then gradually reduce the pressure in the system to further advance the polymerization reaction. By gradually increasing the degree of vacuum in the reaction system midway through the process, the work required at the start of the reaction can be started under normal pressure, and the by-product aryl alcohol or alkyl alcohol can be easily removed from the reaction system. Specifically, the pressure reduction step is preferably carried out at a rate of about 100 to 10,000 Pa / min, more preferably 500 to 7,000 Pa / min, and even more preferably 1,000 to 4,000 Pa / min.

[0118] As is clear from the above description, it is not necessary to always carry out the polymerization reaction under reduced pressure in the polymerization step, and it is preferable to reduce the pressure in the reaction system after the polymerization reaction has progressed, preferably to a certain extent, from a state in which the raw materials are at least in a molten state. For example, as will be described later, since it is preferable to gradually increase the reaction temperature in the polymerization step, it is preferable to start the depressurization step after the temperature of the reaction system has been raised to a certain extent, for example, at 150°C or higher, more preferably at 180°C or higher.

[0119] In the polymerization step, the temperature in the above-mentioned polymerization reaction is preferably within a range of 150 to 300°C, more preferably 180 to 290°C, and even more preferably 200 to 280°C. Thus, in the polymerization step, it is preferable to polymerize the oxysilane compound or diaryloxysilane compound with the diol compound or aromatic diol compound at a reaction temperature higher than 200° C. In addition, it is preferable to carry out the polymerization step under reduced pressure. In order to gradually generate and remove the by-product aryl alcohol or alkyl alcohol, it is preferable to gradually increase the temperature from room temperature to a reaction temperature set within the above-mentioned range. The temperature increase is preferably carried out at a rate of about 1 to 10°C / min, more preferably 2 to 8°C / min, and even more preferably 3 to 7°C / min.

[0120] The time for the polymerization step is determined as appropriate, taking into consideration the type of target polysiloxane compound and reaction conditions such as pressure and temperature, but for example, the total time for the polymerization step is within 1 to 10 hours. More specifically, the reaction time before the above-mentioned reduction in pressure in the reaction system is 0.1 to 3 hours, preferably 0.5 to 2 hours, and the reaction time after the reduction in pressure is 0.5 to 8 hours, preferably 1 to 6 hours.

[0121] Furthermore, the oxysilane compound and the diol compound have good compatibility with each other, and the polycarbonate copolymer can be produced without using a solvent in the polymerization process. In this way, since a solvent such as a halogen-based solvent is not required, the environmental load caused by the polymerization reaction can be reduced and the polymerization process can be simplified.

[0122] Furthermore, the by-products generated in the polymerization step are the above-mentioned aryl alcohols, alkyl alcohols, etc., which can be easily removed from the reaction system and do not require special treatment for safety reasons, etc. Therefore, the method for producing a polysiloxane compound according to the present invention can reduce the environmental load compared to conventional production methods that, for example, produce an acid as a by-product or use an acid.

[0123] In the polymerization step, the ratio of the molar amount of the transesterification catalyst to the molar amount of the aromatic diol compound (molar ratio: i.e., the value of the molar amount of the transesterification catalyst / the molar amount of the aromatic diol compound) is 0.01 μmol / mol to 16,000 μmol / mol (1.0 × 10 -8 ~1.6×10 -2 ) The molar ratio is 0.05 to 10,000 μmol / mol (5.0 × 10 -8 ~1.0×10 -2 ), and more preferably 0.5 to 5000 μmol / mol (5.0 × 10 -7 ~5.0×10 -3 ), and more preferably 0.80 to 1000 μmol / mol (8.0 × 10 -7 ~1.0×10 -3), and particularly preferably 1.0 to 100 μmol / mol (1.0 × 10 -6 ~1.0×10 -4 )

[0124] In the polymerization step, the molar ratio of the diol compound such as an aromatic diol compound to the oxysilane compound such as a diaryloxysilane compound (i.e., the value of the number of moles of oxysilane compound / the number of moles of diol compound) is, for example, 0.8 to 1.3, preferably 0.9 or more and 1.2 or less, more preferably 0.95 or more and 1.18 or less, and even more preferably 1.00 or more and 1.16 or less.

[0125] Next, the polysiloxane compound according to the present invention will be described in detail. [(V) Polysiloxane compound] The polysiloxane compound produced by the process of the present invention is a polymer having siloxane structural units as described above, and specific examples thereof include the following. That is, the polyarylenesiloxane compound is a polymer having at least a siloxane constituent unit represented by any one of the following formulas (1-1') to (1-4'). [ka]

[0126] In formulas (1-1') to (1-4'), R 1 and R 2 each independently represents 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 1 and R 2 When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. Also, R 1 and R 2When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0127] In formulas (1-1') and (1-2'), R 3 ~R 10 each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent. R 3 ~R 10 When the alkyl group is an alkyl group which may have a substituent, it preferably has a total of 1 to 10 carbon atoms, more preferably has a total of 1 to 4 carbon atoms, and particularly preferably has a total of 1 or 2 carbon atoms. R 3 ~R 10 When the alkyl group is an alkenyl group which may have a substituent, it preferably has a total of 2 to 10 carbon atoms, more preferably has a total of 2 to 6 carbon atoms, and particularly preferably has a total of 2 to 4 carbon atoms. Also, R 3 ~R 10 When the aryl group is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms.

[0128] In formulas (1-1') to (1-3'), each Z1 is independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In formulas (1-1') to (1-3'), J1 and K1 each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, for example, 1 or 2. In formula (1-3'), A1 and A2 each independently represent -O- or -CH-. L1 and L2 each independently represent an integer of 0 or more and 3 or less, and L1 and L2 are preferably 1 or 2. In the formulas (1-1′) and (1-2′), each X is independently a single bond or any of the structural formulas represented by the following formula (2). [ka] In formula (2), R 11 , and R 12 each independently represents hydrogen, halogen, 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, or R 11 and R 12 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 or more and 5,000 or less. R 11 , and R 12 are preferably each independently hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent. In formula (2), a and b are each independently 0 or an integer of 1 or more and 5000 or less, and a and b are preferably integers of 1000 or less, more preferably integers of 500 or less, and even more preferably integers of 100 or less. In the siloxane structural unit, X is R 11 and R 12 are preferably bonded to each other to form a fluorene ring structure.

[0129] The siloxane constitutional unit preferably contains at least one represented by the following formula (1'). [ka]

[0130] R in formula (1') 1 and R2 The siloxane structure containing the following is introduced from the above-mentioned oxysilane compound. In formula (1'), R 1 and R 2 Regarding the preferred options, R in the above formulas (1-1′) to (1-4′) 1 and R 2 is the same as:

[0131] The above-mentioned R 1 and R 2 Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. R in formula (1') 1 and R 2 Preferred specific examples of the group include a methyl group, a phenyl group, a vinyl group, and a propyl group.

[0132] In formula (1'), R 3 ~R 10 Regarding the preferred options, R in the above formulas (1-1′) to (1-4′) 1 and R 2 is the same as: The above-mentioned R 3 ~R 10 Examples of the substituent include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group.

[0133] In formula (1′), m represents an integer of 10 or more and 1,000 or less. The value of m in formula (1′) is preferably 20 or more and 800 or less, and more preferably 30 or more and 500 or less.

[0134] In formula (1), X is R in the above formulas (1-1′) and (1-2′). 1 and R 2 is the same as:

[0135] The weight average molecular weight of the polysiloxane compound such as the polyarylenesiloxane compound is preferably 5,000 to 300,000, more preferably 10,000 to 300,000, even more preferably 10,000 to 200,000, and particularly preferably 10,000 to 100,000, for example, 20,000 to 90,000, more preferably 30,000 to 80,000, and particularly preferably 40,000 to 70,000.

[0136] The glass transition temperature (Tg) of the polysiloxane compound such as the polyarylenesiloxane compound according to JIS K 7121 is, for example, 40 to 200°C, and preferably 45 to 160°C.

[0137] In the above-mentioned polysiloxane compound, i.e., a polysiloxane compound having siloxane constituent units represented by any of Formulas (1-1) to (1-4) and Formulas (1-1') to (1-4'), the weight-average molecular weight is 5,000 to 300,000, and the total content of cyclic units represented by the following formula (5-4) is preferably 4.0 wt% or less, more preferably 3.0 wt% or less, even more preferably 2.0 wt% or less, and particularly preferably 1.0 wt% or less, based on the total weight of the polysiloxane compound. If the total content of these low molecular weight cyclic compounds, such as cyclic dimers, is within the above range, the properties of the polysiloxane compound are good, particularly when used in optical applications. [ka] In formula (5-4), the structural unit represented by formula (5-4) and other structural units may be arranged arbitrarily. That is, structural units other than the structural unit whose structure is clearly indicated as formula (5-4) may be included, but in any case, the total value of m is 2 to 10, preferably 2 to 5, more preferably 2 or 3, for example 2. R 1 , R 2 , R 3 ~R10 and X are the same as those in formula (1-1) and formula (1-2). In formula (5-4), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms, which may have a substituent. In formula (5-4), 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, more preferably an integer of 0 or more and 2 or less, for example, 1 or 2.

[0138] The lower limit of the low-molecular-weight cyclic compounds in the polysiloxane compound, similar to the content of the low-molecular-weight compounds in the polycarbonate copolymer having a weight-average molecular weight of 1,000 or less, is not particularly important, but is about 0.7% by weight. However, even if the low-molecular-weight compounds are contained in an amount of 0.001%, 0.01%, or 0.1% by weight or more, the properties of the polysiloxane compound, particularly when used for optical purposes, are not affected, and fluidity may be improved. Therefore, the lower limit of the content of the low-molecular-weight compounds in the polysiloxane compound having a weight-average molecular weight of 1,000 or less may be 0.001%, 0.01%, or 0.1% by weight.

[0139] The content of the low-molecular-weight cyclic compounds in the polysiloxane compound is a value calculated by adding up the contents of several low-molecular-weight compounds as impurities from the peak area ratio of each component obtained by GPC analysis, as will be described in detail later in the Examples. That is, as will be described in detail later, it can be calculated from a predetermined GPC area ratio, similar to the measurement of the proportion of low-molecular-weight compounds having a molecular weight of 1,000 or less in a polycarbonate copolymer.

[0140] Among the cyclic compounds represented by formula (5-4), a specific example is the cyclic dimer represented by the following formula (5-4'), and it has been confirmed that the molecular structure of the cyclic dimer represented by formula (5-4') and such a cyclic dimer can be contained in a polysiloxane compound. [ka]

[0141] The polysiloxane compound may also contain a total content of cyclic compounds represented by the following formulas (6-1) and (6-2). These cyclic compounds are considered to be cyclic dimers formed as a side reaction of the polymerization reaction for producing the polysiloxane compound. The content of these cyclic dimers in the polysiloxane compound is preferably 2.0 wt% or less, more preferably 1.5 wt% or less, even more preferably 1.0 wt% or less, and particularly preferably 0.5 wt% or less, based on the total weight of the polysiloxane compound. [ka] In formulas (6-1) and (6-2), the structural units represented by these formulas may be arranged arbitrarily with other structural units. That is, structural units other than those explicitly shown in formulas (6-1) and (6-2) may be included, but in either case, the total value of n is 2 to 10, preferably 2 to 5, more preferably 2 or 3, for example 2. In formulas (6-1) and (6-2), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In formulas (6-1) and (6-2), i and ii each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, for example, 1 or 2. In addition, in the formulas (6-1) and (6-2), R 1 and R 2 , R 3 ~R 10 , Z1 and Z2, J1, K1 and X are as described above.

[0142] The lower limit of the total content of the cyclic dimers represented by formulas (6-1) and (6-2) contained in the polysiloxane compound is not particularly limited, and may be, for example, 0.001% by weight, 0.01% by weight, or 0.1% by weight. The presence of a small amount of the cyclic dimer can contribute to improving the flowability of the polysiloxane compound during molding.

[0143] Specific examples of the compounds of formula (6-1) and (6-2) include cyclic compounds of the following formulas (6-1') and (6-2'). [ka] In addition, in formulas (6-1') and (6-2'), R 1 and R 2 , R 3 ~R 10 and R 30 ~R 33 , Z1 and Z2, J1, K1 and X are as described above.

[0144] The polysiloxane compound preferably has a 1% mass loss thermal decomposition temperature of 415°C or lower, more preferably a 1% mass loss thermal decomposition temperature of 400°C or lower, even more preferably a 1% mass loss thermal decomposition temperature of 385°C or lower, and particularly preferably a 1% mass loss thermal decomposition temperature of 370°C or lower.

[0145] In the polysiloxane compound, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the polysiloxane compound is preferably 0.1 to 20 mass%, more preferably 1.0 to 15 mass%, even more preferably 2.0 to 12 mass%, and particularly preferably 3.0 to 10 mass% (for example, 3.1 mass% or more, or more than 3.1 mass% and 9.8 mass% or less).

[0146] Next, the composition according to the present invention, that is, the composition containing the above-mentioned polysiloxane compound and the like, will be described in detail.

[0147] <3. Composition> The composition of the present invention contains the above-mentioned polysiloxane compound and a polycarbonate resin, such as a polycarbonate resin that is completely or substantially free of a siloxane structure.

[0148] The type of polycarbonate resin contained in the composition together with the polysiloxane compound is not particularly limited, as long as it contains an -[OR-OCO]- unit containing a carbonate bond in the molecular main chain (where R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). Polycarbonate resins that do not fall under the category of the polysiloxane compounds described above may contain polyester carbonate. Similarly, the polyester carbonate is not particularly limited, as long as it contains an -[OR-OC]- unit containing a carbonate bond in the molecular main chain (where R is as described above).

[0149] The weight average molecular weight of the polycarbonate resin contained in the composition together with the polysiloxane compound is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.

[0150] The composition of the present invention may contain a resin other than a polycarbonate resin, preferably a thermoplastic resin. The type of thermoplastic resin is not particularly limited, but examples thereof include polycarbonate resin, polyester carbonate resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide.

[0151] In the composition, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the composition is preferably 0.1 to 20 mass%, more preferably 0.2 to 15 mass%, and particularly preferably 0.3 to 10 mass%. The proportion of the total Si content in the composition can be adjusted by the proportion of siloxane constituent units to all constituent units in the above-mentioned polycarbonate resin, or by the amount of resin or Si content mixed with the polycarbonate resin. For example, Q1, which is the Q value of a composition containing a polysiloxane compound measured under conditions of 280°C and 160 kgf, is preferably 120% or more (20% or more higher) than Q2, which is the Q value of only the polycarbonate resin contained in the composition measured under the same conditions. The Q1 value of the entire composition is more preferably 130% or more, even more preferably 140% or more, and particularly preferably 150% or more, for example 160% or more, of the Q2 value of only the polycarbonate. Furthermore, for example, in the case of a composition containing 5% by mass of a polysiloxane compound, Q1, which is the Q value measured under conditions of 280°C and 160 kgf, is preferably 140% or more (40% or more higher) than Q2, which is the Q value measured under the same conditions for only the polycarbonate resin contained in the composition. The Q1 value of the entire composition is more preferably 150% or more, even more preferably 160% or more, and particularly preferably 170% or more, for example 180% or more, of the Q2 value for only the polycarbonate.

[0152] A composition with excellent characteristics can be produced by using a polysiloxane compound with a high Si content. By mixing a polysiloxane compound having a Si content of, for example, 0.1 mass% or more with a resin that is substantially free of siloxane structural units, preferably a polycarbonate resin, the resulting composition can have both excellent impact resistance and flowability.

[0153] Compositions containing polysiloxane compounds may contain phenolic compounds that may be produced as by-products of the polymerization reaction, as well as unreacted oxysilane compounds and diol compounds. The impurities phenolic compounds and DPC can reduce the strength of molded articles and cause odors, so their content is preferably as low as possible. Therefore, the content of phenolic compounds, oxysilane compounds, and diol compounds may be reduced to an undetectable level, but from the perspective of productivity, they may be included in the composition within a range that does not impair the effects. Furthermore, by including a predetermined amount of residual monomer, for example, 1 to 1,000 ppm by weight, preferably 10 to 900 ppm, and more preferably 20 to 800 ppm, based on the total weight of the composition, the effect of improving fluidity during molding can be obtained, and the plasticity of the resin when molten can be improved.

[0154] <4. Molded body> Next, a molded article containing a polysiloxane compound such as the polyarylenesiloxane compound described above will be described. The molded article of the present invention is obtained by molding a polysiloxane compound such as the polyarylenesiloxane compound described above. The molding method for the molded article is not particularly limited, and examples of the molded article include injection molded articles, press molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and pressure molded articles.

[0155] The optical lens according to the present invention is obtained by molding the polysiloxane compound of the present invention or a composition containing the polysiloxane compound. The polysiloxane compound of the present invention is suitable for optical applications and is suitably used for optical films, optical lenses, etc. The optical lens of the present invention has a refractive index, Abbe number, etc. within ranges suitable for a lens.

[0156] (Regarding secondary ingredients) Deactivator After the polymerization reaction is complete, the catalyst may be removed or deactivated from the polycarbonate copolymer and polysiloxane compound of the present invention in order to maintain thermal stability and hydrolytic stability. A method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, and esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, and dioctyl phosphate. Suitable examples of the deactivator include phosphate esters such as phosphate esters (e.g., monooctyl phosphate, diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc.), phosphonic acids (e.g., diethyl phenylphosphonate, etc.), phosphines (e.g., triphenylphosphine, bis(diphenylphosphino)ethane, etc.), boric acids (e.g., boric acid, phenylboric acid, etc.), aromatic sulfonates (e.g., tetrabutylphosphonium dodecylbenzenesulfonate, etc.), organic halides (e.g., stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, etc.), alkyl sulfates (e.g., dimethyl sulfate, etc.), and organic halides (e.g., benzyl chloride, etc.). These deactivators may be used in an amount of, for example, 0.001 to 50 times, and preferably 0.01 to 30 times, the amount of the catalyst.

[0157] additives <Stabilizer> A stabilizer may be added to the polycarbonate copolymer and polysiloxane compound of the present invention. Examples of stabilizers include heat stabilizers and antioxidants. When blended, the stabilizer is added in an amount of preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.02 parts by mass or more, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound, and is preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and even more preferably 1.0 part by mass or less. The stabilizer may be one type, or two or more types. When two or more types are used, the total amount is preferably within the above range.

[0158] <<Heat stabilizer>> Examples of heat stabilizers include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds. Also included are at least one compound selected from the group consisting of (a) a phosphite ester compound in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group having 1 to 25 carbon atoms, (b) phosphorous acid, and (c) tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphonite.Specific examples of the phosphite ester compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, trisnonylphenyl phosphite, tris(octylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol. Examples of suitable diphosphite include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyldiphenyl phosphite, distearylpentaerythritol diphosphite, tricyclohexyl phosphite, diphenylpentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more. Examples of organic phosphite compounds include "ADK STAB 1178 (trade name, the same applies hereinafter)," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by Adeka Corporation; "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.; and "IRGAFOS 168" manufactured by BASF. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate. When a heat stabilizer is added, the amount thereof is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.03 part by mass or more, and is preferably 1 part by mass or less, more preferably 0.7 part by mass or less, even more preferably 0.5 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. The heat stabilizer may be contained in one kind only, or in two or more kinds. When two or more kinds are contained, it is preferable that the total amount is in the above range.

[0159] <<Antioxidants>> Examples of the antioxidant include phenol-based antioxidants, hindered phenol-based antioxidants, bisphenol-based antioxidants, and polyphenol-based antioxidants.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)propionate]methane, tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N' -Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxazone) Examples of suitable hydroxybenzyl compounds include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, and the like. Examples of phenolic antioxidants include "Irganox 1010" (registered trademark, the same applies hereinafter) and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by Adeka Corporation. When an antioxidant is added, the amount thereof is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 1 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. The antioxidant may be contained alone or in combination with two or more kinds. When two or more kinds are contained, the total amount is preferably in the above range.

[0160] The polycarbonate copolymer and polysiloxane compound of the present invention may contain various additives within the scope of the present invention. Examples of additives 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 it is preferable to include at least one of a flame retardant and a mold release agent. Furthermore, antistatic agents, fluorescent brighteners, anti-fogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc. may be added as long as they do not significantly impair the desired physical properties.

[0161] <Flame retardant> The polycarbonate copolymer and polysiloxane compound of the present invention may contain various additives within the scope of the present invention. As a flame retardant, an organic metal salt-based flame retardant, a phosphorus-based flame retardant, a silicone-based flame retardant, etc. may be contained. Examples of flame retardants that can be used in the present invention include the flame retardants (flame retardant compositions) described in paragraphs 0085 to 0093 of JP 2016-183422 A, the contents of which are incorporated herein by reference.

[0162] <UV absorber> Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, as well as organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, hindered amine compounds, and phenyl salicylate compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.In particular, specific examples of the benzotriazole compound include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole. Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]phenol 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl)-methylene]-propanediol acid dimethyl ester, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol phenol, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], [methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate, and the like can be mentioned.Among the above, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] are preferred. Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Specific examples of phenyl salicylate-based UV absorbers include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol and 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol. Specific examples of hindered amine-based UV absorbers include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate. When the ultraviolet absorber is added, the amount thereof is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and is preferably 3 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. The ultraviolet absorber may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0163] <Release agent> Examples of the release agent include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specific examples include at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number-average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Here, the term "aliphatic carboxylic acid" also encompasses alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, and more preferred are saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those described above can be used as the aliphatic carboxylic acids in the esters of aliphatic carboxylic acids and alcohols. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and saturated aliphatic monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferred. Here, aliphatic compounds also include alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, etc. The above-mentioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, or may be a mixture of multiple compounds.Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture primarily composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Aliphatic hydrocarbons having a number-average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbon compounds may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxidized polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number average molecular weight is preferably 200 to 5000. These aliphatic hydrocarbons may be a single substance or a mixture of substances with various constituent components and molecular weights, as long as the main component is within the above range. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination. When a release agent is added, the amount thereof is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. The release agent may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0164] <Coloring agent> The colorant may be either a dye or a pigment, and examples thereof include inorganic pigments, organic pigments, organic dyes, etc. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as iron blue. Examples of organic pigments and organic dyes as colorants include phthalocyanine-based pigments and dyes (dyes and pigments are referred to as "pigments" below) such as copper phthalocyanine blue and copper phthalocyanine green; azo-based pigments and dyes such as nickel azo yellow; condensed polycyclic pigments and dyes such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl-based pigments and dyes. Among these, titanium oxide, carbon black, cyanine, quinoline, anthraquinone, and phthalocyanine-based pigments and dyes are preferred from the viewpoint of thermal stability. Furthermore, the colorant may be used in the form of a masterbatch with a polystyrene resin, a polycarbonate resin, or an acrylic resin, for the purposes of improving handling during extrusion and improving dispersibility in the resin composition. When a colorant is added, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, and 0.1 parts by mass or more, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. Only one colorant may be used, or two or more colorants may be used. When two or more colorants are used, the total amount is preferably within the above range.

[0165] Molded products other than lenses There are no limitations on the shape, pattern, color, or dimensions of molded articles obtained using polycarbonate copolymers or polysiloxane compounds, and these may be arbitrarily selected depending on the intended use. Specific examples of molded articles include electrical and electronic devices, office automation (OA) equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and sundries, lighting equipment parts, and various household electrical appliance parts, as well as housings, containers, covers, storage compartments, and cases for electrical appliances, and covers and cases for lighting fixtures. Examples of electrical and electronic devices include personal computers, game consoles, television receivers, display devices such as liquid crystal displays and plasma display devices, printers, copiers, scanners, fax machines, electronic organizers and personal digital assistants (PDAs), electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, recording medium drives and readers, mice, numeric keypads, CD (Compact Disc) players, MD (MiniDisc) players, and portable radio and audio players. Further examples of molded articles include illuminated signs, liquid crystal backlights, illuminated displays, traffic signs, signboards, screens, reflectors, meter parts and other automobile parts (on-vehicle parts), toys, and ornaments. The polycarbonate copolymer and polysiloxane compound of the present invention have excellent impact resistance, high fluidity when melted, and can be formed into molded articles having a fine structure, and therefore can be suitably used as in-vehicle electric / electronic parts, mechanical parts, and vehicle parts, such as automobile interior panels, automobile lamp lenses, automobile inner lenses, automobile lens protective covers, and automobile light guides.

[0166] Molding method for molded body The method for producing the molded article of the present invention is not particularly limited, and any molding method commonly used for resins such as polycarbonate resins can be used. Examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted and other hollow molding methods, molding using an insulated mold, molding using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, and press molding. Molding methods using a hot runner system can also be used.

[0167] Other resins The polycarbonate copolymer and polysiloxane compound of the present invention may contain, as necessary, resins other than the polycarbonate copolymer and polysiloxane compound of the present invention, as long as the desired physical properties are not significantly impaired. Examples of such other resins include polycarbonate resins other than the polycarbonate copolymer and polysiloxane compound of the present invention, thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate resin (PTT resin), and polybutylene terephthalate resin (PBT resin); styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer (MS resin); and methyl methacrylate-acrylic rubber-styrene copolymer. Examples of suitable elastomers include core / shell elastomers such as copolymers (MAS), polyester-based elastomers, and other elastomers; polyolefin resins such as cyclic cycloolefin resins (COP resins) and cyclic cycloolefin (COP) copolymer resins; polyamide resins (PA resins); polyimide resins (PI resins); polyetherimide resins (PEI resins); polyurethane resins (PU resins); polyphenylene ether resins (PPE resins); polyphenylene sulfide resins (PPS resins); polysulfone resins (PSU resins); polymethacrylate resins (PMMA resins); and polycaprolactone. [Example]

[0168] [Example of polycarbonate resin] <Measurement of polystyrene equivalent weight average molecular weight (Mw)> Using GPC (gel permeation chromatography), a calibration curve was created using standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution = 1) and chloroform as the developing solvent. The elution time and molecular weight value of each peak from the measured standard polystyrene were plotted, and a cubic fit was performed to create a calibration curve. Then, based on the obtained calibration curve, the weight average molecular weight (Mw) was calculated as a polystyrene equivalent value using the following formula. [Calculation formula] Mw=Σ(W i ×M i ) / Σ(W i ) (In the above formula, i represents the i-th division point when dividing the molecular weight M, W i is the i-th weight, M i represents the i-th molecular weight. Also, the molecular weight M represents the molecular weight in polystyrene equivalent at the same elution time on the calibration curve.) [Measurement conditions] Equipment: Shimadzu Labsolutions Columns: Guard column (Shodex GPC KG 4A) x 1, analytical column (Shodex GPC K-805L) x 2 Solvent: Chloroform (HPLC grade) ·Injection volume: 10μL Sample concentration: 2000 ppm Solvent flow rate: 1 mL / min ·Measurement temperature: 40℃ Detector: RI

[0169] <Measurement of the content of low molecular weight compounds with a weight average molecular weight (Mw) of 1,000 or less> The proportion of low molecular weight compounds with Mw of 1,000 or less in the polycarbonate resin was calculated from the ratio of the area from retention time 20.5 min to 21.5 min to the area from 0 min to 21.5 min (GPC area ratio) based on the data obtained by GPC analysis under the above-mentioned conditions. That is, GPC analysis was carried out under the conditions described in the section <Measurement of polystyrene-equivalent weight-average molecular weight (Mw)>, and the content ratio of low-molecular-weight compounds (B / A × 100(%)) was measured based on the ratio of the GPC area (A) of the peak with a retention time of 21.5 minutes or less, which is considered to correspond to the amount of all compounds contained in the polycarbonate resin sample, to the GPC area (B) of the peak confirmed with a retention time between 20.5 minutes and 21.5 minutes, which is considered to correspond to the amount of low-molecular-weight compounds with a weight-average molecular weight of 1,000 or less.

[0170] <Measurement of glass transition temperature (Tg)> A test piece weighing 5 to 12 mg was weighed into an AI autosampler sample container (RDC aluminum pan, a cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm) and the top of the sample container was sealed with an AI autosampler cover. The measurements were 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 reference material in the reference cell. The measurement sample, adjusted to 30°C, was heated to 280°C at 20°C / min, and then cooled to 30°C at 20°C / min. The temperature was then increased to 280°C at 10°C / min, and measurements were performed. Measurement equipment: Differential scanning calorimeter (DSC) (product name "DSC-7020", manufactured by Hitachi High-Tech Science Corporation)

[0171] <Measurement of low molecular weight compounds (phenol (PhOH), bisphenol A (BPA), dimethyldiphenoxysilane (DMDPS), diphenyl carbonate (DPC)> 10 g of the sample was dissolved in 60 g of dichloromethane to prepare a resin solution, and 150 g of ethanol was added dropwise to the stirred resin solution over 30 minutes. The precipitate was filtered off using No. A5 filter paper, and the filtrate was concentrated using an evaporator to obtain oligomer component a. The obtained precipitate was dissolved in 60 g of dichloromethane to prepare a resin solution, and 150 g of ethanol was added dropwise to obtain the precipitate and oligomer component b. The obtained oligomer components a and b were dissolved in dichloromethane to prepare a 1000 μg / mL solution, which was then analyzed and quantified by GC / FID. The quantitative values ​​are calculated in terms of 2,2-bis(4-hydroxyphenyl)propane, and are determined from a calibration curve of 2,2-bis(4-hydroxyphenyl)propane prepared in advance. [GC / FID measurement conditions] Equipment: Shimadzu GC2025 Column: Capillary column DB-35, 30 mm x 0.25 mm x 0.25 μm Heating conditions: 40℃ - 300℃ (5 min hold), 10℃ / min Injection port temperature: 300°C, injection volume: 1.0 μL (split ratio 1:20) Carrier gas: He ·Air flow rate: 400mL / min ·H2 flow rate: 40mL / min Make-up gas: 30mL / min Standard substance: 2,2-bis(4-hydroxyphenyl)propane

[0172] <Measurement of cyclic dimer> The content of the above-mentioned cyclic dimer contained in the polycarbonate copolymer was measured as follows. A 20g sample of polycarbonate copolymer was dissolved in 120g of dichloromethane to prepare a resin solution, and 200g of ethanol was added dropwise to the stirred resin solution over 30 minutes. The precipitate was filtered off using No. A5 filter paper, and the filtrate was concentrated using an evaporator to obtain oligomer component A and precipitate A. Subsequently, the obtained precipitate A was dissolved in 120 g of dichloromethane to prepare a resin solution, and 200 g of ethanol was added dropwise to the stirred resin solution over 30 minutes. The precipitate was separated by filtration using No. A5 filter paper, and the filtrate was concentrated using an evaporator to obtain oligomer component B and precipitate B. Subsequently, the obtained precipitate B was dissolved in 120 g of dichloromethane to prepare a resin solution, and 200 g of ethanol was added dropwise to the stirred resin solution over 30 minutes. The precipitate was filtered off using No. A5 filter paper, and the filtrate was concentrated using an evaporator to obtain oligomer component C and precipitate C. The resulting oligomer components A, B, and C were dissolved in dichloromethane to prepare a 1000 μg / mL solution, and the cyclic dimer was analyzed by GC-Q-MS / FID. The quantitative values ​​were calculated in terms of 2,2-bis(4-hydroxyphenyl)propane using a calibration curve for 2,2-bis(4-hydroxyphenyl)propane prepared in advance. [GC-Q-MS / FID measurement conditions] Instrument: Agilent Technologies Agilent-7890B / Agilent-5975C MSD Inert XL MSD with TAD Column: DB-5MS, 15mm x 0.25mm x 0.1μm ·Restrictor(MS):0.18mm×1.44mm ·Restrictor(FID):0.18mm×0.53mm Heating conditions: 50°C (2 min hold) - 320°C (15 min hold), 20°C / min ·Inlet temperature: 300℃ Injection volume: 1.0 μL (split ratio 1:10) Carrier gas: He FID / MS ratio: 1 / 1 ·Aux temperature: 300℃ Scan Range: m / z 33-700 Scan rate: 2.22 scans / s ·FID temperature: 300℃ ·H2 flow rate: 30mL / min ·Air flow rate: 400mL / min Make-up gas: 25mL / min Standard substance: 2,2-bis(4-hydroxyphenyl)propane Quantitation of cyclic dimer: Quantitation from peak intensity at 16.6 min

[0173] <Liquidity (Q value)> Melt flow volume (cm) per unit time measured at 280°C and a load of 160 kg -3 / sec) (the melt flow volume was measured using a Shimadzu Corporation CFT-500D model (nozzle diameter 1 mm x nozzle length 10 mm), and the value per unit time was calculated from a stroke of 7.0 to 10.0 mm).

[0174] <Charpy impact test> The Charpy impact strength (kJ / m) of the molded test piece was measured in accordance with JIS-K7111. 2 ) was measured.

[0175] <Measuring method of refractive index (nd)> Refractive index (nd): A 3 mm thick rectangular piece made of the polycarbonate copolymer produced in the example was measured using an Abbe refractometer according to the method of JIS-K-7142. <Measuring method of Abbe number (νd)> The refractive index of a 3 mm thick rectangular piece made of the polycarbonate resin produced in the examples was measured at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C using an Abbe refractometer, and the Abbe number was calculated using the following formula. νd=(nd-1) / (nF-nC) nd: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0176] (Synthesis Example 1) Synthesis of dimethyldiphenoxysilane Dimethyldiphenoxysilane was synthesized with reference to the method described in US2012 / 184702. 176.34 g (1.87 mol) of phenol was stirred at 50°C under a N2 atmosphere, and 113.24 g (0.88 mol) of dimethyldichlorosilane was added dropwise over 30 minutes. One hour after the completion of the addition, by-products were distilled off at 170°C under a reduced pressure of 200 hPa. The reaction solution was cooled to room temperature, and the product was dissolved in 300 mL of dichloromethane. The product dissolved in dichloromethane was washed twice with 300 mL of 10% NaOH solution, and the organic layer was extracted. The organic layer was washed twice with 300 mL of water, and the organic layer after washing was extracted. Residual water was removed with anhydrous magnesium sulfate, and then the dichloromethane was distilled off using an evaporator to obtain an oily component. The resulting oily component was analyzed by H-NMR and confirmed to be dimethyldiphenoxysilane (H-NMR (CDCl, 500 MHz, δ; ppm) = 0.378 (s; 6H), 6.942, 6.944 (d; 4H), 6.959, 6.961, 6.995 (t; 2H), 7.230, 7.245, 7.257 (t; 4H)). The molar yield was 66%.

[0177] (Example A-1) 104.97g (0.46mol) of 2,2-bis(4-hydroxyphenyl)propane, 4.58g (0.02mol) of dimethyldiphenoxysilane, 101.46g (0.47mol) of diphenyl carbonate, and 2.0µmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 300ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 190°C and stirred for 20 minutes. After that, the transesterification reaction was carried out over 1 hour and 20 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260 ° C and the vacuum level was reduced to 2 hPa or less. This was maintained for another 1 hour and 30 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted to change stepwise 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, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 44,373. The Tg of the copolymer was measured using DSC and found to be 136° C. The weight loss of the copolymer was measured using TG-DTA and found to be 411° C. for 1% weight loss.

[0178] (Example A-2) 72.85g (0.32mol) of 2,2-bis(4-hydroxyphenyl)propane, 7.9g (0.032mol) of dimethyldiphenoxysilane, 65.86g (0.31mol) of diphenyl carbonate, and 0.6µmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 300ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1.5 hours while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260°C and the vacuum level was reduced to 4 hPa or less, and this was maintained for another 1.5 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 48,035. The Tg of the copolymer was measured using DSC and found to be 129°C. The Q value of the copolymer was measured and found to be 75 (×10 -2 cm 3 / sec).

[0179] (Example A-3) 21.69 g (0.10 mol) of 2,2-bis(4-hydroxyphenyl)propane, 9.52 g (0.39 mol) of dimethyldiphenoxysilane, 13.5 g (0.63 mol) of diphenyl carbonate, and 7.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 4 hPa or less. This was maintained for another 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Furthermore, during the reduced pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 54,007. The Tg of the copolymer was measured using DSC and found to be 101°C. The Q value of the copolymer was measured and found to be 114(×10 -2 cm 3 / sec).

[0180] (Example A-4) 30.69 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 25.46 g (0.10 mol) of dimethyldiphenoxysilane, 9.96 g (0.046 mol) of diphenyl carbonate, and 7.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 4 hPa or less. This was maintained for another 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 63,068. The Tg of the copolymer was measured using DSC and found to be 75°C.

[0181] (Example A-5) 30.63 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 31.05 g (0.13 mol) of dimethyldiphenoxysilane, 5.04 g (0.024 mol) of diphenyl carbonate, and 7.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 4 hPa or less. This was maintained for another 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 49,161. The Tg of the copolymer was measured using DSC and found to be 62°C.

[0182] (Examples A-6 to A-14) Copolymers were produced in the same manner as in Example A-1, except that the raw material compounds were changed as shown in Table 1 below. The properties of the obtained copolymers are shown in Table 1. [Table 1]

[0183] (Example A-15) 2,2-bis(4-hydroxyphenyl)propane (2310g, 10.13mol), dimethyldiphenoxysilane (1849.26g, 7.58mol), diphenyl carbonate (753.04g, 3.52mol), and cesium carbonate (14.0µmol / mol) as a catalyst (catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 10L reactor equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 40 minutes. After that, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260°C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 1 hour and 15 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Note that during the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 12,000 Pa, 8,000 Pa, 4,000 Pa, and 100 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 208,939. The Tg of the copolymer was measured using DSC and found to be 74.2° C. The weight loss of the copolymer was measured using TG-DTA and found to be 337.1° C. for 1% weight loss.

[0184] (Example A-16) 2,2-bis(4-hydroxyphenyl)propane (2497g, 10.95mol), dimethyldiphenoxysilane (1997.20g, 8.19mol), diphenyl carbonate (813.00g, 3.80mol), and cesium carbonate (3.0µmol / mol) as a catalyst (catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 10L reactor equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 45 minutes. After that, over 2 hours and 30 minutes, the phenol distilled from the reaction system was condensed and removed using a cooling tube while the transesterification reaction was carried out. The system was then heated to 260°C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the vacuum reduction, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 6,000 Pa, 4,000 Pa, and 100 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 81,885. The Tg of the copolymer was measured using DSC and found to be 75.1° C. The weight loss of the copolymer was measured using TG-DTA and found to be 380.6° C. for 1% weight loss. The amounts of low molecular weight compounds contained in the copolymer were determined using GC, and the copolymer contained 415 ppm of PhOH, 475 ppm of BPA, 122 ppm of DMDPS, and 44 ppm of DPC.

[0185] (Reference example) According to the aforementioned cyclic dimer measurement method, 19.99 g of the copolymer obtained in Example A-16 was dissolved in 121.22 g of dichloromethane, and 196 g of ethanol was added dropwise to the stirred resin solution over 30 minutes. The precipitate was filtered using No. A5 filter paper, and the filtrate was concentrated using an evaporator to obtain 0.652 g of oligomer component A. The precipitate was again dissolved in dichloromethane, and ethanol was added dropwise to separate the precipitate and oligomer components. This procedure was repeated twice (obtaining 0.268 g of obtained oligomer component B, 0.177 g of obtained oligomer component C, and 18.99 g of copolymer reprecipitate, i.e., precipitate). The obtained oligomer components A, B, and C were dissolved in dichloromethane to obtain a 1000 μg / mL solution. Analysis by GC-Q-MS / FID revealed that the cyclic dimer content of the reprecipitated copolymer was 0.71 wt%. The Q value of the siloxane-containing polycarbonate copolymer obtained in Example A-16 was 117 (×10 -2 cm 3 / sec), and the Q value of the siloxane-containing polycarbonate copolymer reprecipitate obtained in the reference example was 74 (× 10 -2 cm 3 / sec). It can be seen that the inclusion of the cyclic dimer increases the Q value and provides high fluidity. [Table 2]

[0186] (Example A-17) 30.99g (0.07mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 13.01g (0.05mol) of diphenyldimethoxysilane, 5.28g (0.02mol) of diphenyl carbonate, and 15.0µmol / mol of cesium carbonate catalyst (catalyst amount is the relative molar amount to 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) were placed in a 100ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190°C and melted, and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour and 10 minutes while condensing and removing the phenol and methanol distilled from the reaction system using a cooling tube, and the system was heated to 260°C and the vacuum level was reduced to 2 hPa or less. This was maintained for another 15 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the vacuum reduction, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 115,683. The Tg of the copolymer was measured using DSC and found to be 110.9° C. The weight loss of the copolymer was measured using TG-DTA and found to be 351.4° C. for 1% weight loss.

[0187] (Example A-18) 24.71 g (0.071 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 18.00 g (0.074 mol) of diphenyldimethoxysilane, 0.831 g (0.004 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 9,9-bis(4-hydroxyphenyl)fluorene) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190°C and melted, and stirred for 15 minutes. After that, the transesterification reaction was carried out over 1 hour and 20 minutes while condensing and removing the phenol and methanol distilled from the reaction system using a cooling tube. The temperature in the system was reduced to 260°C and the vacuum level was reduced to 2 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 12,992. The Tg of the copolymer was measured using DSC and found to be 165.5° C. The weight loss of the copolymer was measured using TG-DTA and found to be 361.1° C. for 1% weight loss.

[0188] (Example A-19) 17.07g (0.04mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 12.06g (0.03mol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 12.99g (0.05mol) of diphenyldimethoxysilane, 5.26g (0.02mol) of diphenyl carbonate, and 15.0µmol / mol of cesium carbonate catalyst (catalyst amount is the relative molar amount relative to the sum of the molar amounts of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene) were placed in a 100ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 200°C and stirred for 30 minutes. After that, over 1 hour and 20 minutes, the phenol and methanol distilled from the reaction system were condensed and removed using a cooling tube while the transesterification reaction was carried out. The system was then heated to 260°C, the vacuum level was reduced to 2 hPa or less, and the reaction was held for another 1 hour and 20 minutes to obtain a browned, transparent polycarbonate copolymer having an arylenesiloxane structure. During the vacuum reduction, the pressure was adjusted to change stepwise from atmospheric pressure to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 23,272. The Tg of the copolymer was measured using DSC and found to be 140.4° C. The weight loss of the copolymer was measured using TG-DTA and found to be 349.4° C. for 1% weight loss.

[0189] (Example A-20) 24.71 g (0.071 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 1.80 g (0.007 mol) of dimethyldiphenoxysilane, 16.21 g (0.066 mol) of diphenyldimethoxysilane, 0.83 g (0.004 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 9,9-bis(4-hydroxyphenyl)fluorene) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 210°C and melted, and stirred for 25 minutes. After that, the transesterification reaction was carried out over 1 hour and 25 minutes while condensing and removing the phenol and methanol distilled from the reaction system using a cooling tube. The temperature in the system was reduced to 260°C and the vacuum level was reduced to 2 hPa or less, and this was maintained for another hour to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 28,050. The Tg of the copolymer was measured using DSC and found to be 171.4° C. The weight loss of the copolymer was measured using TG-DTA and found to be 339.1° C. for 1% weight loss.

[0190] (Example A-21) 10.22 g (0.07 mol) of isosorbide, 17.60 g (0.07 mol) of diphenyldimethoxysilane, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to isosorbide) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 100°C and stirred for 10 minutes. The transesterification reaction was then carried out over 1 hour and 55 minutes while the methanol distilling from the reaction system was condensed and removed using a cooling tube. The system was then heated to 200°C, the vacuum level was reduced to 2 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a yellowed, transparent arylenesiloxane. During the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 30,000 Pa, 10,000 Pa, 6,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 9,125. The Tg of the copolymer was measured using DSC and found to be 71.1° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 256.2° C. for 1% weight loss.

[0191] (Example A-22) 17.50 g (0.07 mol) of bis(4-hydroxyphenyl)sulfone, 17.42 g (0.07 mol) of diphenyldimethoxysilane, and 30.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to bis(4-hydroxyphenyl)sulfone) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 220°C and stirred for 25 minutes. After that, the transesterification reaction was carried out over 1 hour and 15 minutes while condensing and removing the methanol distilling from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 2 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a slightly reddish, transparent arylenesiloxane. Note that during the reduced pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 12,806. The Tg of the arylenesiloxane was measured using DSC and found to be 123.6° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 384.7° C. for 1% weight loss.

[0192] (Example A-23) 31.00 g (0.07 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 18.98 g (0.08 mol) of diphenyldimethoxysilane, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190°C and melted, and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour and 10 minutes while condensing and removing the methanol distilling from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 2 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a colorless and transparent arylenesiloxane. Note that during the reduced pressure, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 3,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 46,225. The Tg of the arylenesiloxane was measured using DSC and found to be 97.4° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 350.6° C. for 1% weight loss.

[0193] (Example A-24) 24.71 g (0.07 mol) of 9,9-bis(4-hydroxyphenyl)fluorene, 18.95 g (0.08 mol) of diphenyldimethoxysilane, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 9,9-bis(4-hydroxyphenyl)fluorene) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 190°C and stirred for 15 minutes. After that, over 1 hour and 30 minutes, the methanol distilling from the reaction system was condensed and removed using a cooling tube while the transesterification reaction was carried out. The system was then heated to 260°C, the vacuum level was reduced to 2 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a yellowed, transparent arylenesiloxane. During the vacuum reduction, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 3,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 27,028. The Tg of the arylenesiloxane was measured using DSC and found to be 169.7° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 364.8° C. for 1% weight loss.

[0194] (Example A-25) 15.26 g (0.07 mol) of bis(4-hydroxyphenyl) sulfide, 17.42 g (0.07 mol) of diphenyldimethoxysilane, and 30.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles to bis(4-hydroxyphenyl) sulfide) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 190°C and stirred for 15 minutes. After that, the transesterification reaction was carried out over 2 hours and 15 minutes while condensing and removing the methanol distilling from the reaction system using a cooling tube, and the system was heated to 260°C and the reduced pressure was reduced to 2 hPa or less, and this was maintained for another 1 hour and 20 minutes to obtain a colorless and transparent arylenesiloxane. Note that during the reduced pressure, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 56,797. The Tg of the arylenesiloxane was measured using DSC and found to be 73.2° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 391.6° C. for 1% weight loss.

[0195] Table 3 shows the results of Examples A-15 to A-25 and Reference Example described above. [Table 3]

[0196] (Example A-26) 37.73 g (0.07 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene, 19.47 g (0.07 mol) of dimethyldiphenoxysilane, and 30.0 μmol / mol of sodium bicarbonate (catalyst amount is the relative molar amount to 9,9-bis(6-hydroxynaphthyl)fluorene) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 210 °C and melted, and stirred for 30 minutes. The phenol distillate was then removed over a condenser tube over the course of 1 hour and 30 minutes to allow for transesterification, and the temperature in the system was reduced to 280°C, the vacuum level was reduced to 2 hPa or less, and the pressure was maintained for another 1 hour and 50 minutes to obtain a yellowed, transparent arylenesiloxane. The pressure was adjusted in stages from atmospheric pressure to 30,000 Pa, 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 39,353. The Tg of the arylenesiloxane was measured using DSC and found to be 138° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 369.3° C. for 1% weight loss.

[0197] (Example A-27) 61.04 g (0.33 mol) of 4,4'-dihydroxybiphenyl, 89.64 g (0.37 mol) of dimethyldiphenoxysilane, and 3.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to 4,4'-dihydroxybiphenyl) were placed in a 200 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 220°C and stirred for 60 minutes. After that, the phenol distilled from the reaction system was condensed and removed in a cooling tube over a period of 1 hour. A colorless, transparent arylenesiloxane was obtained by carrying out an ester exchange reaction, reducing the temperature in the system to 260°C and the degree of vacuum to 1 hPa or less, and maintaining this for two hours. The pressure was adjusted so that it changed stepwise from atmospheric pressure to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 6,000 Pa, 4,000 Pa, and 100 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 46,000. The Tg of the arylenesiloxane was measured using DSC and found to be 70.4° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 378° C. for 1% weight loss.

[0198] (Example A-28) 79.71 g (0.43 mol) of 4,4'-dihydroxybiphenyl, 107.42 g (0.44 mol) of diphenyldimethoxysilane, and 3.0 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to 4,4'-dihydroxybiphenyl) were placed in a 200 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 220°C and stirred for 30 minutes. After that, over a period of 2 hours, the methanol distilled from the reaction system was condensed and removed using a cooling tube while the transesterification reaction was carried out. The system was then heated to 260°C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 2 hours to obtain a colorless, transparent arylenesiloxane. During the vacuum reduction, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 17,000. The Tg of the arylenesiloxane was measured using DSC and found to be 110° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 345° C. for 1% weight loss.

[0199] (Example A-29) 39.06 g (0.21 mol) of 4,4'-dihydroxybiphenyl, 38.58 g (0.16 mol) of dimethyldiphenoxysilane, 15.60 g (0.07 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 4,4'-dihydroxybiphenyl) were placed in a 300 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 220°C and melted, and stirred for 20 minutes. After that, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260 ° C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 10 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 33,710. The Tg of the copolymer was measured using DSC and found to be 78.8° C. The weight loss of the copolymer was measured using TG-DTA and found to be 357° C. for 1% weight loss.

[0200] (Example A-30) 39.06 g (0.21 mol) of 4,4'-dihydroxybiphenyl, 35.00 g (0.14 mol) of diphenyldimethoxysilane, 15.60 g (0.07 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate (catalyst amount: relative molar amount to 4,4'-dihydroxybiphenyl) were placed in a 300 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 220°C and stirred for 20 minutes. After that, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing the methanol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260 ° C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 10 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Note that during the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 11,845. The Tg of the copolymer was measured using DSC and found to be 120° C. The weight loss of the copolymer was measured using TG-DTA and found to be 363° C. for 1% weight loss.

[0201] (Example A-31) 26.18 g (0.07 mol) of 2,2'-bishydroxyethoxy-1,1'-binaphthyl, 19.82 g (0.08 mol) of dimethyldiphenoxysilane, and 30 μmol / mol of sodium bicarbonate as a catalyst (the catalyst amount is the relative molar amount to 2,2'-bishydroxyethoxy-1,1'-binaphthyl) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 210°C and stirred for 35 minutes. After that, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube. The system was then heated to 260°C and the reduced pressure was reduced to 1 hPa or less, and this was maintained for another 1 hour and 30 minutes to obtain a colorless, transparent arylenesiloxane. Note that during the reduced pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 19,975. The Tg of the arylene siloxane was measured using DSC and found to be 54° C. The weight loss of the arylene siloxane was measured using TG-DTA and found to be 296° C. for 1% weight loss.

[0202] (Example A-32) 26.18g (0.07mol) of 2,2'-bishydroxyethoxy-1,1'-binaphthyl, 5.40g (0.03mol) of diphenyl carbonate, 12.65g (0.05mol) of dimethyldiphenoxysilane, and 30µmol / mol of sodium bicarbonate as a catalyst (the catalyst amount is the relative molar amount to 2,2'-bishydroxyethoxy-1,1'-binaphthyl) were placed in a 100ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 220°C and stirred for 1 hour. After that, over 1 hour and 10 minutes, the phenol distilled from the reaction system was condensed and removed using a cooling tube while the transesterification reaction was carried out. The temperature in the system was reduced to 260 ° C, the vacuum level was reduced to 1 hPa or less, and this was maintained for another 1 hour and 20 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the decompression, the pressure was adjusted to change stepwise from atmospheric pressure to 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 32,178. The Tg of the copolymer was measured using DSC and found to be 74° C. The weight loss of the copolymer was measured using TG-DTA and found to be 317° C. for 1% weight loss.

[0203] (Example A-33) 10.22 g (0.07 mol) of isosorbide, 5.20 g (0.02 mol) of diphenyl carbonate, 12.86 g (0.05 mol) of dimethyldiphenoxysilane, and 15.0 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to isosorbide) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 200°C and stirred for 30 minutes. After that, the transesterification reaction was carried out over 1 hour and 20 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the temperature in the system was reduced to 260 ° C and the vacuum level was reduced to 2 hPa or less. This was maintained for another 1 hour and 30 minutes to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduction in pressure, the pressure was adjusted to change stepwise from atmospheric pressure to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 39,378. The Tg of the copolymer was measured using DSC and found to be 55° C. The weight loss of the copolymer was measured using TG-DTA and found to be 242° C. for 1% weight loss.

[0204] (Example A-34) 21.28 g (0.07 mol) of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 19.82 g (0.08 mol) of dimethyldiphenoxysilane, and 30.0 μmol / mol of sodium bicarbonate (catalyst amount is the relative molar amount to 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 210°C and melted, followed by stirring for 30 minutes. After that, the transesterification reaction was carried out over 1 hour and 50 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube. The system was then heated to 260°C and the reduced pressure was reduced to 2 hPa or less, and this was maintained for another hour to obtain a colorless, transparent arylenesiloxane. During the reduced pressure reduction, the pressure was adjusted to change stepwise from atmospheric pressure to 30,000 Pa, 25,000 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the arylenesiloxane was measured using GPC and found to be 15,708. The Tg of the arylenesiloxane was measured using DSC and found to be 51° C. The weight loss of the arylenesiloxane was measured using TG-DTA and found to be 236° C. for 1% weight loss.

[0205] (Example A-35) 21.28 g (0.07 mol) of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 5.20 g (0.02 mol) of diphenyl carbonate, 12.86 g (0.05 mol) of dimethyldiphenoxysilane, and 30.0 μmol / mol of sodium bicarbonate (catalyst amount is relative to 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) were placed in a 100 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 210°C and melted, followed by stirring for 30 minutes. After that, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing the phenol distilled from the reaction system using a cooling tube, and the system was heated to 260 ° C and the vacuum level was reduced to 2 hPa or less. This was maintained for another hour to obtain a transparent polycarbonate copolymer having an arylenesiloxane structure. During the vacuum reduction, the pressure was adjusted so that it changed stepwise from atmospheric pressure to 30,000 Pa, 25,000 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 68,693. The Tg of the copolymer was measured using DSC and found to be 63° C. The weight loss of the copolymer was measured using TG-DTA and found to be 252° C. for 1% weight loss.

[0206] (Comparative example A-1) 17.51 ​​g (0.08 mmol) of 2,2-bis(4-hydroxyphenyl)propane, 20.93 g (0.09 mol) of dimethyldiphenoxysilane, and 7 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the phenol distilled from the reaction system was condensed and removed using a cooling tube over a period of 1 hour while the ester exchange reaction was carried out. The temperature inside the system was then reduced to 260°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 2 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 63,257. The Tg of the copolymer was measured using DSC and found to be 54°C.

[0207] (Comparative example A-2) The Mw of polycarbonate (Mitsubishi Gas Chemical Company, Iupilon S-3000) was measured using GPC and found to be 51,252. The Tg of the polycarbonate was measured using DSC and found to be 149°C.

[0208] (Comparative example A-3) Comparative Example A-3 was a polycarbonate resin using Iupizeta EP6000 manufactured by Mitsubishi Gas Chemical Company, Inc., i.e., BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) as the diol compound. The polycarbonate resin of Comparative Example A-3 had an Mw of 30,000, a Q value of 97 × 10 cm / sec, a Tg of 142°C, a refractive index (nd) of 1.638, and an Abbe number (vd) of 23.5. Compared with Comparative Example A-3, Examples A-17, 19, and 23, which used the same diol compound, were confirmed to have improved fluidity (increased Q value) without significantly changing the optical properties.

[0209] The results of Examples A-26 to A-35 and Comparative Examples A-1 and A-2 are shown in Table 4. [Table 4]

[0210] (Example A-36) 10 g of the polycarbonate copolymer obtained in Example A-3 and 190 g of polycarbonate (Iupilon S-3000, manufactured by Mitsubishi Gas Chemical Company) were kneaded and extruded at 280°C using a kneading extruder (Labo Plastomill 4C150, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The Q value of the obtained composition was 11.9 (×10 -2 cm 3 The composition was dried in a dryer at 110°C for 12 hours, and then a test piece for the Charpy impact test was molded using an injection molding machine ("C-Mobile" manufactured by Shinko Selvic Co., Ltd.) at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was carried out in accordance with JIS-K7111, resulting in a value of 60.9kJ / m 2 It was.

[0211] (Example A-37) 10 g of the polycarbonate copolymer obtained in Example A-4 and 190 g of polycarbonate (Iupilon S-3000, manufactured by Mitsubishi Gas Chemical Company) were kneaded and extruded at 280°C using a kneading extruder (Labo Plastomill 4C150, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The Q value of the obtained composition was 14.1 (×10 -2 cm 3 The composition was dried in a dryer at 110°C for 12 hours, and then a test piece for the Charpy impact test was molded using an injection molding machine ("C-Mobile" manufactured by Shinko Selvic Co., Ltd.) at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was carried out in accordance with JIS-K7111, resulting in a value of 65.8kJ / m 2 It was.

[0212] (Example A-38) 150 g of the polycarbonate copolymer obtained in Example A-16 and 1850 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E-2000) were mixed at a resin temperature of 280 ° C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH), and then injection molded under conditions of a mold temperature of 80 ° C and a holding pressure of 90 MPa to form a test piece for Charpy impact testing. A notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 70.1 kJ / m 2The Q value of the obtained composition was 5.5 (×10 -2 cm 3 / sec). (Example A-39) 300 g of the polycarbonate copolymer obtained in Example A-16 and 1700 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E-2000) were mixed at a resin temperature of 280 ° C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH), and then injection molded under conditions of a mold temperature of 80 ° C and a holding pressure of 90 MPa to form a test piece for Charpy impact test. A notched Charpy impact test was performed in accordance with JIS-K7111, and the result was 76.7 kJ / m 2 The Q value of the obtained composition was 8.1 (×10 -2 cm 3 / sec). (Example A-40) 600 g of the polycarbonate copolymer obtained in Example A-16 and 1,400 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E-2000) were mixed at a resin temperature of 280 ° C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH), and then injection molded under conditions of a mold temperature of 80 ° C and a holding pressure of 90 MPa to form a test piece for Charpy impact test. A notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 6.9 kJ / m 2 The Q value of the obtained composition was 17.2 (× 10 -2 cm 3 / sec).

[0213] (Comparative example A-4) The Q value of polycarbonate (Mitsubishi Gas Chemical, Iupilon S-3000) is 8.0 (× 10 -2 cm 3 In addition, after the polycarbonate was dried in a dryer at 110°C for 12 hours, a test piece for the Charpy impact test was molded using an injection molding machine ("C-Mobile" manufactured by Shinko Selvic) at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was conducted in accordance with JIS-K7111, resulting in a value of 62.9kJ / m 2It was.

[0214] (Comparative example A-5) 2000g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E-2000) was mixed at a resin temperature of 300°C using a kneading extrusion injection molding machine (Sodick TR100EH high-speed injection molding machine), and then injection molded at a mold temperature of 80°C and a holding pressure of 90MPa to form test pieces for the Charpy impact test. A notched Charpy impact test was conducted in accordance with JIS-K7111, resulting in a value of 72.7kJ / m. 2 The Q value of the obtained composition was 2.8 (× 10 -2 cm 3 / sec).

[0215] The results of Examples A-36 to A-40 and Comparative Examples A-4 and A-5 are shown in Table 5 below. [Table 5]

[0216] [Examples of Polysiloxane Compounds] Examples relating to polysiloxane compounds will be described below. <Polystyrene equivalent weight average molecular weight (Mw)> Using GPC (gel permeation chromatography), a calibration curve was created using chloroform as the developing solvent and standard polystyrene of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, the GPC retention time was calculated. <Glass transition temperature (Tg)> It was measured by a differential scanning calorimeter (DSC). In the obtained DSC curve, the temperature was determined from the intersection of a line drawn by extending the low-temperature baseline toward the high-temperature side and a tangent drawn at the point where the gradient of the curve in the step-like change portion of the glass transition is maximum.

[0217] (Synthesis Example 2) Synthesis of dimethyldiphenoxysilane 7.5 g (20.2 mmol, Si molar amount: 101.0 mmol) of decamethylcyclopentasiloxane, 21.6 g (101.0 mmol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200°C for 60 minutes under a nitrogen atmosphere. Subsequently, the reaction mixture was cooled to 40°C and then distilled under reduced pressure at 150°C and a reduced pressure of 4 hPa to obtain 23.7 g of a colorless oily component. The obtained oily component 1 Analysis by H-NMR confirmed that it was dimethyldiphenoxysilane. 1 H-NMR (CDCl3, 500 MHz, δ; ppm) = 0.378 (s; 6H), 6.942, 6.944 (d; 4H), 6.959, 6.961, 6.995 (t; 2H), 7.230, 7.245, 7.257 (t; 4H)). The molar yield was 96.0%.

[0218] (Example B-1) 30.03 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 33.50 g (0.14 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount: relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, followed by stirring for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 26,699.

[0219] (Example B-2) 30.03 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 34.40 g (0.14 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, and stirred for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 33,521.

[0220] (Example B-3) 30.05 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 34.69 g (0.14 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount: relative moles to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, followed by stirring for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 30,603.

[0221] (Example B-4) 30.03 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 35.10 g (0.14 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, and stirred for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 36,940.

[0222] (Example B-5) 30.08 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 36.00 g (0.15 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount: relative moles to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, followed by stirring for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 39,994. The Tg of the polyarylenesiloxane was measured using DSC and found to be 49°C.

[0223] (Example B-6) 30.03 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 37.38 g (0.15 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 180°C and melted, and stirred for 30 minutes. Thereafter, an ester exchange reaction was carried out over 1.5 hours while condensing and removing the phenol distilling from the reaction system using a cooling tube. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 34,196.

[0224] (Example B-7) 17.51 ​​g (0.077 mol) of 2,2-bis(4-hydroxyphenyl)propane, 20.93 g (0.086 mol) of dimethyldiphenoxysilane, and 7 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the phenol distilled from the reaction system was condensed and removed using a cooling tube over a period of 1 hour while the ester exchange reaction was carried out. The temperature inside the system was then reduced to 260°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 63,257. The Tg of the polyarylenesiloxane was measured using DSC and found to be 54°C.

[0225] (Synthesis Example 3) 14.9 g (0.19 mol) of octaphenylcyclotetrasiloxane represented by the following formula (3), 16.1 g (0.08 mol) of diphenyl carbonate, and 33 mg (0.1 mmol) of cesium carbonate as a catalyst were stirred at 200°C for 10 minutes under a nitrogen atmosphere. After cooling to room temperature, 20 g of heptane was added to the solidified reaction mixture, and the mixture was heated to 90°C and filtered while hot. The resulting filtrate was left at room temperature for 3 days to precipitate white crystals. 10 g of heptane cooled to 5°C was added, and the mixture was filtered. The crystals on the filter paper were removed and dried at 40°C and a reduced pressure of 1 hPa for 45 hours, yielding 24.1 g of a white powder. The resulting powder was 1 Analysis by H-NMR confirmed that it was diphenyldiphenoxysilane. 1 H-NMR (CDCl, 500 MHz, δ; ppm) = 6.915, 6.927, 6.939, 6.952, 6.965 (p; 6H), 7.142, 7.155, 7.169 (t; 4H), 7.354, 7.366, 7.379 (t; 4H), 7.425, 7.437, 7.449 (t; 2H), 7.750, 7.762 (d; 4H). The molar yield was 81.1%. [ka]

[0226] (Example B-8) 11.75 g (0.052 mol) of 2,2-bis(4-hydroxyphenyl)propane, 20.25 g (0.055 mol) of diphenyldiphenoxysilane, and 20 μmol / mol of cesium carbonate as a catalyst (the catalyst amount is the relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the phenol distilled from the reaction system was condensed and removed using a cooling tube over a period of 1 hour while the ester exchange reaction was carried out. The temperature inside the system was then reduced to 260°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 24,482. The Tg of the polyarylenesiloxane was measured using DSC and found to be 89°C.

[0227] (Comparative example B-1) 20.00 g (0.088 mol) of 2,2-bis(4-hydroxyphenyl)propane and 23.62 g (0.097 mol) of dimethyldiphenoxysilane were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. Thereafter, the temperature inside the system was set to 240°C and the pressure was reduced to 4 hPa (400 Pa) or less to attempt a transesterification reaction, but the raw materials were distilled off and the reaction did not proceed.

[0228] (Comparative example B-2) 21.28 g (0.093 mol) of 2,2-bis(4-hydroxyphenyl)propane, 25.12 g (0.10 mol) of dimethyldiphenoxysilane, and 11 μmol / mol of cesium carbonate (catalyst amount: relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. Thereafter, the temperature inside the system was raised to 240°C under normal pressure over 1.5 hours and maintained at that temperature for a further 1.5 hours, yielding a colorless and transparent polyarylenesiloxane. The Mw of the polyarylenesiloxane was measured using GPC and found to be 1,547.

[0229] (Comparative example B-3) 29.96 g (0.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 36.10 g (0.15 mol) of dimethyldiphenoxysilane, and 16,600 μmol / mol of cesium carbonate as a catalyst (or 16.6 mmol / mol: the catalyst amount is the relative molar amount to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 100 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to melt at 180°C and stirred for 30 minutes. After that, the phenol distilled from the reaction system was condensed and removed using a cooling tube over a period of 1 hour while the ester exchange reaction was carried out. The temperature inside the system was then reduced to 240°C, the vacuum level was reduced to 4 hPa or less, and this was maintained for a further 1.5 hours to obtain a colorless and transparent polyarylenesiloxane. The Mw of the colorless, transparent polyarylenesiloxane was measured using GPC and found to be 886.

[0230] (Comparative example B-4) 30.75 g (0.14 mol) of 2,2-bis(4-hydroxyphenyl)propane and 36.90 g (0.15 mol) of dimethyldiphenoxysilane were placed in a 100 ml four-neck flask equipped with a stirrer. Immediately thereafter, the temperature inside the system was raised to 240°C and the pressure reduced to 4 hPa (400 Pa) or less to attempt transesterification, but the raw materials were distilled off and the reaction did not proceed.

[0231] The results of each example and comparative example are shown in Table 6 below. [Table 6]

Claims

1. an oxysilane compound containing at least one of a diaryloxysilane compound which is any one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, and a dialkoxysilane compound which is any one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane; a polymerization step of polymerizing a diol compound including an aromatic diol compound or an alicyclic diol compound, In the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure using a transesterification catalyst while removing the resulting aryl alcohol and / or alkyl alcohol, and the amount of the transesterification catalyst relative to the diol compound is 0.01 μmol / mol to 16,000 μmol / mol in terms of molar ratio; the transesterification catalyst comprises an alkali metal compound and / or an alkaline earth metal compound; A method for producing a polysiloxane compound, which produces a poly(arylene / alkylene)siloxane compound having a weight average molecular weight of 10,000 to 300,000, which contains a structural unit represented by any one of the following formulas (1-1') to (1-4'): 【Chemistry 1】 (In formulas (1-1') to (1-4'), R １ , and R ２ each independently represents 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 ~R １０ and R ３０ ~R ３３ each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Z １ and Z ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, J １ each independently represents an integer of 0 to 5, K １ each independently represents an integer of 0 to 5, A １ and A ２ each independently represents -O- or -CH-; L １ and L ２ each independently represents an integer of 0 to 3, m １ ~m ４ represents the total number of constitutional units in each formula, and is a natural number of 10 to 1000, X is a single bond or any one of the structural formulas represented by the following formula (2): 【Chemistry 2】 (In the formula, R １１ , and R １２ each independently represents hydrogen, halogen, 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, or R １１ and R １２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5,000.

2. Z １ and Z ２ are each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent, J １ each independently represents an integer of 0 to 2, K １ each independently represents an integer of 0 to 2, A method for producing the polysiloxane compound according to claim 1.

3. The X is R １１ and R １２ 3. The method for producing a polysiloxane compound according to claim 1, wherein the polysiloxane compound has siloxane structural units that represent a fluorene ring structure formed by bonding together:

4. The method includes a polymerization step of polymerizing a diaryloxysilane compound containing at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane with an aromatic diol compound, In the polymerization step, the diaryloxysilane compound and the aromatic diol compound are polymerized in a molten state under reduced pressure using a transesterification catalyst while removing aryl alcohol, and the amount of the transesterification catalyst relative to the aromatic diol compound is 0.01 μmol / mol to 16,000 μmol / mol in terms of molar ratio; the transesterification catalyst comprises an alkali metal compound and / or an alkaline earth metal compound; A method for producing a polysiloxane compound, which produces a polyarylenesiloxane compound having a weight average molecular weight of 10,000 to 300,000 and containing a constituent unit represented by the following formula (1): 【Transformation 3】 (In the formula, R １ , and R ２ each independently represents 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 ~R １０ each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; m represents a natural number between 10 and 1000, X is any one of the structural formulas represented by the following formula (2): 【Chemistry 4】 (In the formula, R １１ , and R １２ each independently represents hydrogen, halogen, 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, or R １１ and R １２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5,000.

5. The method for producing a polysiloxane compound according to any one of claims 1 to 4, wherein the reaction temperature in the polymerization step is in the range of 150°C or higher and 300°C or lower.

6. 6. The method for producing a polysiloxane compound according to claim 1, wherein the reaction pressure in the polymerization step is 101,300 Pa or less.

7. 7. The method for producing a polysiloxane compound according to claim 1, further comprising a depressurizing step of gradually reducing the reaction pressure to 400 Pa or less in the polymerization step.

8. 8. The method for producing a polysiloxane compound according to claim 4, wherein in the polymerization step, the amount of the transesterification catalyst relative to the aromatic diol compound is 0.1 to 100 μmol / mol in terms of molar ratio.

9. The method for producing a polysiloxane compound according to any one of claims 1 to 8, wherein the alkali metal compound and / or alkaline earth metal compound comprises at least one of a carbonate, a hydroxide, an oxide, and an alkoxy compound.

10. 10. The method for producing a polysiloxane compound according to claim 9, wherein the alkali metal compound and / or alkaline earth metal compound is a carbonate.

11. The method for producing a polysiloxane compound according to any one of claims 1 to 10, wherein no solvent is used in the polymerization step.

12. The method for producing a polysiloxane compound according to any one of claims 4 to 11, wherein a molar ratio of the diaryloxysilane compound to the aromatic diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

13. 4. The method for producing a polysiloxane compound according to claim 1, wherein in the polymerization step, the oxysilane compound and the diol compound are polymerized at a reaction temperature higher than 200°C and / or under reduced pressure.

14. The method for producing a polysiloxane compound according to any one of claims 4 to 13, wherein in the polymerization step, the diaryloxysilane compound and the aromatic diol compound are polymerized at a reaction temperature higher than 200°C and / or under reduced pressure.

15. A polysiloxane compound containing a structural unit represented by any one of formulas (1-1) to (1-4), having a weight-average molecular weight of 5,000 to 300,000, and containing cyclic units represented by formula (5-4) in a total content of 0.001% by weight or more and 3.0% by weight or less. 【Transformation 5】 (In formulas (1-1) to (1-4), R １ , and R ２ each independently represents 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 ~R １０ and R ３０ ~R ３３ each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; Z １ and Z ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, J １ each independently represents an integer of 0 to 5, K １ each independently represents an integer of 0 to 5, A １ and A ２ each independently represents -O- or -CH-; L １ and L ２ each independently represents an integer of 0 to 3, X is a single bond or any one of the structural formulas represented by the following formula (2): 【Transformation 6】 (In the formula, R １１ , and R １２ each independently represents hydrogen, halogen, 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, or R １１ and R １２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5,000. 【Transformation 7】 (In formula (5-4), the constitutional unit represented by formula (5-4) may be arranged arbitrarily with other constitutional units, and the total value of m is 2 to 10, R １ , and R ２ each independently represents 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 ~R １０ each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; X １ and X ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, m represents an integer from 2 to 10; X is a single bond or any one of the structural formulas represented by the following formula (2): 【Transformation 8】 (In formula (2), R １１ , and R １２ each independently represents hydrogen, halogen, 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, or R １１ and R １２ are bonded to each other to form a carbon atom which may have a substituent. represents a carbocyclic or heterocyclic ring having a prime number of 1 to 20; a and b each independently represent 0 or an integer of 1 to 5,000.

16. The polysiloxane compound according to claim 15, wherein the total content of the cyclic compounds of the formulas (6-1) and (6-2) is 2.0% by weight or less. 【Chemistry 9】 (In formulas (6-1) and (6-2), R １ , and R ２ each independently represents 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 ~R １０ and R ３０ ~R ３３ each independently represents hydrogen, halogen, alkoxy, 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 an aryl group having 6 to 30 carbon atoms which may have a substituent; X １ and X ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, i and ii each independently represent an integer of 0 to 5, n represents an integer from 2 to 10; X is a single bond or any one of the structural formulas represented by the following formula (2): 【Chemistry 10】 (In formula (2), R １１ , and R １２ each independently represents hydrogen, halogen, 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, or R １１ and R １２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; a and b each independently represent 0 or an integer of 1 to 5,000.

17. The polysiloxane compound according to claim 15 or 16, having a 1% mass loss thermal decomposition temperature of 415°C or lower.

18. A composition comprising the polysiloxane compound according to any one of claims 15 to 17 and a polycarbonate resin.

19. The composition according to claim 18, wherein the total amount of Si in the composition is 0.1 to 20 mass%.

20. Q is the Q value of the composition measured under conditions of 280°C and 160 kgf. １ is the Q value measured under the same conditions for only the polycarbonate resin contained in the composition, ２ 20. The composition of claim 18, wherein the viscosity of the composition is 120% or more.

21. A molded article comprising the polysiloxane compound according to any one of claims 15 to 17.

22. An optical lens comprising the polysiloxane compound according to any one of claims 15 to 17.

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