Method for producing polycarbonate copolymers and polysiloxane compounds, polycarbonate copolymers, polysiloxane compounds, compositions, and molded articles.

Abstract

The present invention provides a method for efficiently producing a polycarbonate copolymer having siloxane structural units that exhibits excellent impact resistance and high fluidity during melting. [Solution] The method comprises a polymerization step of polymerizing a silane compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound, a carbonate compound, and a diol compound including an aromatic diol compound or an alicyclic diol compound, in the presence of a transesterification catalyst, wherein in the polymerization step, under reduced pressure in a molten state, alcohol derived from the carbonate compound is removed, and a polycarbonate copolymer having siloxane constituent units and polycarbonate constituent units represented by the following formula (1) is produced. TIFF2026076338000105.tif34116

Description

[Technical Field]

[0001] The present invention relates to methods for producing polycarbonate copolymers and polysiloxane compounds, and more particularly to methods for producing polycarbonate copolymers having siloxane structural units, and to polycarbonate copolymers, etc. [Background technology]

[0002] Thermoplastic polycarbonate resins possess excellent impact resistance and mechanical properties, and can be formed into various molded products using simple and highly productive processing methods such as injection molding. They are used in a wide range of industrial fields, including electrical and electronic equipment, office automation equipment, heavy electrical machinery, precision machinery, and automobiles.

[0003] Conventional polycarbonate resins have a drawback of poor fluidity due to their high melt viscosity, which can make injection molding of precision parts and thin materials difficult. Therefore, it has traditionally been necessary to raise the temperature during the molding process. However, molding at high temperatures results in longer molding cycles and higher costs, or the polycarbonate resin may degrade during the molding process. Attempts have been made to improve the fluidity of polycarbonate resins (Patent Documents 1 and 2), but sufficiently high fluidity without compromising the inherent properties of polycarbonate resin (such as impact resistance) has not always been achieved.

[0004] In addition to polycarbonate resins, aromatic polysiloxane polymers, also known as polyarylenesiloxanes, are known as materials for molded products 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 been increasing, 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 hydrochloric acid is produced by reacting dimethyldichlorosilane with bisphenol A in a solvent (Non-Patent Document 1), and a method in which the reaction is carried out in a solvent to which acetic acid has been added (Patent Document 4).

[0006] Furthermore, polycarbonate resins, polysiloxane compounds, etc., that are particularly suitable for specific applications such as optical applications have not yet been realized. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication 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) [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention provides a polycarbonate copolymer having siloxane structural units that exhibits excellent impact resistance and high fluidity during melting, as well as a method for efficiently producing the polycarbonate copolymer.

[0010] Furthermore, the present invention provides safe and efficient methods for producing polycarbonate copolymers having siloxane structural units and polysiloxane compounds. For example, it provides a method for efficiently producing polycarbonate copolymers and polysiloxane compounds such as polyarylenesiloxane without generating corrosive substances such as hydrochloric acid or acetic acid, and without requiring the use of solvents, thereby reducing the environmental burden.

[0011] Furthermore, we provide 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 a polycarbonate copolymer containing siloxane structural units, having excellent impact resistance and high fluidity, as described below, and a method for producing the polycarbonate copolymer. The present invention also provides a method for efficiently producing polycarbonate copolymers and polysiloxane compounds, and polysiloxane compounds, etc., that does not produce environmentally harmful by-products such as acids, can be implemented without solvents, and in particular without solvents that require safety considerations.

[0013] [1] In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silicon compound comprising at least one cyclic siloxane compound and a linear siloxane compound. A silane compound selected from, Carbonate compounds and, The process includes a polymerization step of polymerizing an aromatic diol compound or a diol compound containing an alicyclic diol compound, In the polymerization process, while removing the alcohol derived from the carbonate compound under reduced pressure in a molten state, a method for producing 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).

Chemical formula

Chemical formula

[0014] [4] In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silicon compound comprising at least one cyclic siloxane compound and a linear siloxane compound. A silane compound selected from, The process includes a polymerization step of polymerizing a carbonate compound with a diol compound containing an aromatic diol compound or an alicyclic diol compound. A method for producing a polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), while removing alcohol derived from the carbonate compound under reduced pressure in a molten state during the polymerization process. [ka] (In formula (1), R 1 , and R 2Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X is one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). [ka] (In the formula, R 13 ~R 20 Each independently has hydrogen, halogen, alkoxy, and substituent. A C1-C20 alkyl group may also be a C2-C20 alkenyl group which may have substituents. This represents a group, or an aryl group having 6 to 30 carbon atoms which may have substituents. Y is one of the structural formulas represented by equation (4), [ka] (In the formula, R 21 , and R 22 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R21 and R 22 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive). [5] A method for producing a polycarbonate copolymer according to any one of [1] to [4] above, wherein the transesterification catalyst comprises an alkali metal compound and / or an alkaline earth metal. [6] A method for producing a polycarbonate copolymer according to [5], wherein the alkali metal compound and / or alkaline earth metal compound comprises a carbonate. [7] A 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 molar ratio. -7 ~1.0×10 -2 The method for producing a polycarbonate copolymer as described in any one of the above [1] to [7]. [9] A 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 to 300°C.

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

[11] A 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] A 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] A 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 used in the polymerization step to the number of moles of the diol compound is 0.9 or more and 1.2 or less.

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

[13] , wherein the number of moles of the siloxane constituent units in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate constituent units is 1 to 1000.

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

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

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

[15] , wherein the above is the result of [1] or [1].

[0015]

[17] A polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), wherein the low molecular weight compound with 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 of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 and R 3 ~R 33Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J1 independently represents an integer between 0 and 5, Each K1 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, inclusive. X is either a single bond or one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). [ka] (In formulas (3-1) to (3-4), R 13 ~R 20 and R 40 ~R 51 Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z3 and Z4 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J2 independently represents an integer between 0 and 5, Each K2 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, inclusive. Y is either a single bond or one of the structural formulas represented by formula (4). [ka] (In the formula, R 21 , and R 22 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 21 and R 22 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive).

[18] Z1 to Z4 are each independently alkylene groups having 1 to 3 carbon atoms, which may have substituents. J1 and J2 each independently represent integers between 0 and 2, K1 and K2 each independently represent integers between 0 and 2 (inclusive). The polycarbonate copolymer described in

[17] above.

[19] The above X is R 11 and R 12 A siloxane constituent unit representing a fluorene ring structure formed by the bonding of these units together, and / or, Y is R 21 and R 22 The polycarbonate copolymer according to

[17] or

[18] above, having polycarbonate constituent units that represent a fluorene ring structure formed by the bonding of these units to one another.

[0016]

[20] A polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), wherein the proportion of low molecular weight compounds with 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 of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X is one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). [ka] (In the formula, R 13 ~R 20 Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Y is one of the structural formulas represented by equation (4), [ka] (In the formula, R 21 , and R 22 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 21 and R 22 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive).

[21] The polycarbonate copolymer according to any one of

[17] to

[20] above, wherein the number of moles of the siloxane constituent units in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate constituent units is 1 to 1000.

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

[17] to

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

[23] The polycarbonate copolymer according to

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

[24] The Q value measured under the conditions of 280℃ and 160kgf was 8 (×10 -2 cm 3 s -1 A polycarbonate copolymer according to any one of the above

[17] to

[23] , wherein the above is true.

[0017]

[25] A polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), wherein the total content of the cyclic body represented by formulas (5-1) to (5-3) is 4.0% 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 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 or more and 5 or less, K1 each independently represents an integer of 0 or more and 5 or less, A1 and A2 each independently represent either -O- or -CH-, L1 and L2 each independently represent an integer of 0 or more and 3 or less, X is either a single bond or any of the structural formulas represented by the following formula (2),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

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

[17] to

[25] , wherein the total content of the cyclic compounds of formulas (6-1) to (6-2) is 2.0% by weight or less. [ka] (In equations (6-1) and (6-2), R 1 , and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 and R 30 ~R 33 Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X1 and X2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5 (inclusive). n represents an integer between 2 and 10. X is either a single bond or one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

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

[17] to

[26] , wherein the 1% mass loss thermal decomposition temperature is 415°C or lower.

[28] A composition containing a polycarbonate copolymer and a polycarbonate resin as described in any one of the above items

[17] to

[27] .

[29] The composition according to

[28] , wherein the total Si content in the composition is 0.1 to 20% by mass.

[30] The composition according to either of the above

[28] and

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

[31] A molded article obtained by molding a polycarbonate copolymer as described in any one of the above items

[17] to

[27] .

[32] An optical lens comprising a polycarbonate copolymer as described in any one of the above items

[17] to

[27] .

[33] An optical lens obtained by molding one of the compositions described in any one of the above

[28] to

[30] .

[0018]

[34] A diaryloxysilane compound which is any of a dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane, and an oxysilane compound which is any of a dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, The process includes a polymerization step of polymerizing an aromatic diol compound or a diol compound containing an alicyclic diol compound, In the polymerization step, the oxysilane compound and the diol compound are polymerized under reduced pressure in a molten state using a transesterification catalyst while removing the resulting aryl alcohol and / or alkyl alcohol, wherein the amount of the transesterification catalyst relative to the diol compound is 0.01 μmol / mol to 16,000 μmol / mol in molar ratio. A method for producing polysiloxane compounds, comprising producing poly(arylene / alkylene)siloxane compounds with a weight-average molecular weight of 10,000 to 300,000, which contain a constituent unit represented by any of the following formulas (1-1') to (1-4'). [ka] (In formulas (1-1') to (1-4'), R 1 , and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 and R 30 ~R 33 Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J1 independently represents an integer between 0 and 5, Each K1 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, inclusive. m1 to m4 represent the total number of constituent units in each equation, and are natural numbers between 10 and 1000. X is either a single bond or one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

[35] Z1 and Z2 are each independently a C1-C3 alkylene group which may have substituents, Each J1 independently represents an integer between 0 and 2, K 12 Each of these independently represents an integer between 0 and 2, A method for producing the polysiloxane compound described above

[34] .

[36] The above X is R 11 and R 12 A siloxane constituent unit representing a fluorene ring structure formed by the bonding of these units together, and / or, Y is R 21 and R 22 A method for producing a polysiloxane compound according to

[34] or

[35] , comprising polycarbonate constituent units representing a fluorene ring structure formed by the bonding of these units to one another.

[0019]

[37] A polymerization step is taken to polymerize a diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, diaryldiaryloxysilane, and 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 the 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 molar ratio. A method for producing polysiloxane compounds, comprising 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 of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. m represents a natural number between 10 and 1000, X is one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

[38] A 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 to 300°C.

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

[34] to

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

[41] A 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 molar ratio.

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

[34] to

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

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

[41] , wherein the alkali metal compound and / or alkaline earth metal compound comprises one or more carbonates, hydroxides, oxides, and alkoxy compounds.

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

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

[45] A 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] A 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] A 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 is polymerized with the diol compound or the aromatic diol compound at a reaction temperature higher than 200°C and / or under reduced pressure.

[0020]

[48] ​​A polysiloxane compound containing any of the constituent units represented by formulas (1-1) to (1-4), having a weight-average molecular weight of 5,000 to 300,000, and having a total content of the cyclic product represented by formula (5-4) of 4.0% by weight or less. [ka] (In formulas (1-1) to (1-4), R 1 , and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 and R 30 ~R 33Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J1 independently represents an integer between 0 and 5, Each K1 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, inclusive. X is either a single bond or one of the structural formulas represented by the following formula (2): [ka] (In the formula, R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). [ka] (In equation (5-4), the arrangement of the constituent units represented by equation (5-4) with other constituent units is arbitrary, and the sum of the values ​​of m is between 2 and 10.) R 1 , and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10Each of these independently represents hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X1 and X2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5 (inclusive). m represents an integer between 2 and 10. X is either a single bond or one of the structural formulas represented by the following formula (2): [ka] (In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

[49] The polysiloxane compound described in

[48] above, wherein the total content of the cyclic products of formulas (6-1) to (6-2) is 4.0% by weight or less. [ka] (In equations (6-1) and (6-2), R 1 , and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R 3 ~R 10 and R 30 ~R 33Each independently represents hydrogen, a halogen, an alkoxy group, 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 or more and 5 or less, n represents an integer of 2 to 10, X is either a single bond or any of the structural formulas represented by the following formula (2), [Chemical formula] (In formula (2), R 11 and R 12 each independently represent hydrogen, a 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 represent a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent, formed by bonding to each other, 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 pyrolysis temperature of 415 °C or lower.

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

[34] to

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

[48] to

[50] above, and a polycarbonate resin.

[52] The composition according to

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

[53] The composition according to any one of

[51] and

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

[54] A molded article obtained by molding a polysiloxane compound produced by the manufacturing method described in any one of the above items

[34] to

[46] or a polysiloxane compound described in any one of the above items

[48] to

[50] .

[55] An optical lens comprising a polysiloxane compound manufactured by the manufacturing method described in any one of the above items

[34] to

[46] or a polysiloxane compound described in any one of the above items

[48] to

[50] . [Effects of the Invention]

[0021] The present invention provides a method for producing polycarbonate copolymers that have high fluidity during melting and contain siloxane structural units. Furthermore, the present invention also enables the realization of polycarbonate copolymers with such excellent characteristics, compositions containing polycarbonate copolymers, and molded articles obtained by molding polycarbonate copolymers.

[0022] Furthermore, the method for producing polycarbonate copolymers and polyarylene compounds of the present invention allows for the efficient production of target compounds such as polyarylenesiloxane without generating environmentally harmful by-products such as acids, and without requiring solvents. The present invention also enables the realization of polyarylene compounds such as polyarylenesiloxane with excellent properties. [Modes for carrying out the invention]

[0023] [I. Polycarbonate copolymer] The methods for producing polycarbonate copolymers in the present invention all include a polymerization step in which a silane compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound), a carbonate compound, and an aromatic diol compound are polymerized in the presence of a transesterification catalyst, as will be described in detail later.

[0024] The polymerization reaction described above can be schematically shown below. For example, when diaryloxysilane compound (Si(CH3)2(OPh)2), which is an example of a silane compound and has two methyl groups and a phenoxy group, 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. In other words, it is a polycarbonate copolymer having, for example, a siloxane structural unit produced by the reaction of formula (A) below, and a polycarbonate structural unit produced by, for example, the reaction of formula (B) below. In this polymerization reaction, as described below, alcohols derived from the carbonate compound are produced as by-products. For example, when diaryl carbonate is used as the carbonate compound, aryl alcohols such as phenol (PhOH) are produced. Therefore, in the polymerization step, the mixture of the above components is kept molten, and the polymerization reaction proceeds under reduced pressure while removing the by-product alcohols, such as aryl alcohols 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 compounds] Silane compounds used in the polymerization process are used to form siloxane structural units in polycarbonate copolymers, for example, as shown in formula (A) above. Details regarding the types of silane compounds will be described later, such as -OSi(R 1 R 2) The siloxane structural units containing the O-molecules are not particularly limited as long as they can be formed in the main chain of the polycarbonate copolymer, but are selected from a predetermined diaryloxysilane compound, a predetermined diarykoxysilane compound, and a predetermined silicon compound (siloxane compound).

[0026] In other words, in the polymerization process, a silane compound is used that contains at least one diaryloxysilane compound (details to be described later), at least one dialkoxysilane compound, and at least one silicon compound. As the silane compound, multiple diaryloxysilane compounds may be used in combination, multiple dialkoxysilane compounds may be used in combination, multiple silicon compounds may be used in combination, and a mixture of diaryloxysilane compounds and silicon compounds, a mixture of dialkoxysilane compounds and silicon compounds, or a mixture of diaryloxysilane compounds and dialkoxysilane compounds may be used. Diaryloxysilane compounds will be described below.

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

[0028] Diaryloxysilane compounds are classified under the general formula Si(R a R b When expressed as (OAr)², R a and R b Each of these is independently selected from alkyl groups and aryl groups. a and R b Preferably, each of these is independently an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents, and an aryl group having a total of 6 to 30 carbon atoms. More preferably, R a and R bWhen it is an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2. Also, R a and R b When it is an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0029] Examples of the above-mentioned substituents 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, a mercapto group and the like. R in formula (1) a and R b Preferred specific examples 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 produces a by-product (ArOH) such as phenol. Therefore, the type of the aryloxy group is not particularly limited. However, the aryloxy group preferably has low polarity and molecular weight so that the by-product in the polymerization step can be removed from the reaction system as easily as possible. For example, it is a phenoxy group.

[0031] Specific examples of the dialkyldiaryloxysilane include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane and the like. Specific examples of the diaryldiaryloxysilane include diphenyldiphenoxysilane and the like. Specific examples of the monoalkylmonoaryldiaryloxysilane include methylphenyldiphenoxysilane and the like.

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

[0033] Dialkoxysilane compounds are classified under the general formula Si(R a R b )(OR C When expressed as )², R a and R b Each of these independently corresponds to the R listed in the column for (A-1) diaryloxysilane compounds. a and R b The same alkyl and aryl groups are selected. Furthermore, as is clear from formula (A) above, the alkoxy group (OR) of the silane compound C The alkoxy group is not introduced into the polymer chain of the polycarbonate copolymer, but rather generates by-products such as methanol (MeOH). For this reason, the type of alkoxy group is not particularly limited. However, in order to remove by-products from the reaction system as easily as possible during the polymerization process, the 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. Furthermore, specific examples of monoalkylmonoaryldialkoxysilanes include methylphenyldimethoxysilane.

[0035] (B) Silicon compounds (siloxane compounds) The silicon compounds are described below. Examples of silicon compounds include certain cyclic siloxane compounds and linear siloxane compounds. In other words, either of these may be used as the silane compound in the polymerization process.

[0036] (B-1) Cyclic siloxane compounds Examples of siloxane compounds used in the polymerization process include cyclic siloxane compounds represented by the following formula (5). [ka] In equation (5), R c and R d Each of these independently represents an alkyl group, alkenyl group, or aryl group which may have substituents. c and R d Preferably, each of these is an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents, or an aryl group having a total of 6 to 30 carbon atoms. R c and R d However, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2. Also, R c and R d However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0037] Examples of the substituents mentioned above include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups. R in equation (5) c and R d Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0038] Cyclic siloxane compounds have a siloxane structure, and the siloxane structure is as described above R c Base, and R d -OSi(R) c R d)O-structures are examples. In the polymerization process, such cyclic siloxane compounds are subjected to the -OSi(R c R d The O-part is introduced into the polycarbonate copolymer, the details of which will be described later.

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

[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. Furthermore, 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 compounds Linear siloxane compounds represented by the following formula (6) can also be used as siloxane compounds in the polymerization process. [ka] In equation (6), R e and R f Each of these independently represents an alkyl group or aryl group which may have substituents. e and R f Preferably, each of these is an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents, or an aryl group having a total of 6 to 30 carbon atoms. R e and R f However, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 or 2. Also, R eand R f However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0042] Examples of the substituents mentioned above include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups. R in equation (6) e and R f Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0043] Linear siloxane compounds also have a siloxane structure, and as a siloxane structure, the above-mentioned R e Base, and R f -OSi(R) e R f )O-structures are mentioned. In the polymerization process, the linear siloxane compound -OSi(R e R f The O-part is introduced into the polycarbonate copolymer, the details of which will be described later.

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

[0045] In formula (6), X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have substituents, a hydrocarbon group having a total of 1 to 10 carbon atoms which may have substituents and may have an oxygen atom or a nitrogen atom, or an amino group which may have substituents. Preferably, X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having a total of 1 to 10 carbon atoms which may have substituents, or an alkyl group having a total of 1 to 10 carbon atoms which may have substituents and may have an oxygen atom or a nitrogen atom; more preferably, a hydroxyl group or an alkyl group having a total of 1 to 5 carbon atoms. Examples of substituents on X mentioned above include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, mercapto groups, and the like.

[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. Furthermore, 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 compounds of formula (5) and the linear siloxane compounds represented by formula (6) described below, only a single siloxane compound may be used, or two or more 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 diaryloxysilane compound (A) described above. The silane compounds mentioned above can be synthesized using known methods, or commercially available compounds may be used.

[0048] [(II) Carbonate compounds] Carbonate compounds are used to introduce carbonyl groups (-CO- groups) of polycarbonate constituent units into polycarbonate copolymers, as shown in formula (B) above, which outlines the polymerization reaction. That is, the two -OR groups of a carbonate compound represented by the general formula RO-CO-OR (where R is independently selected from an aryl group, an alkyl group, and an aralkyl group), for example, the two aryloxy groups (ArO- groups) when the carbonate compound is a diaryl carbonate represented by the general formula ArO-CO-OAar, are not introduced into the polymer chain of the polycarbonate copolymer. These -OR groups produce alcohols derived from the carbonate compound as byproducts; for example, a carbonate compound having aryloxy groups (ArO- groups) (monoaryl carbonate or diaryl carbonate) produces aryl alcohols (ArOH), such as phenol, as byproducts.

[0049] Therefore, the types of aryl groups, alkyl groups, and aralkyl groups in the carbonate compound are not particularly limited. However, in order to remove by-products from the reaction system as easily as possible during the polymerization process, it is preferable that the -OR group in the above general formula of the carbonate compound is an aryloxy group (or that the -R group in the above general formula RO-CO-OR is an aryl group), and furthermore, it is preferable that the carbonate compound has low polarity and molecular weight, and the -OR group in the above general formula is, for example, a phenoxy group. Based on the above, it is preferable that in the carbonate compound, one or both of the above-mentioned Ar groups are aryl groups with a total of 10 or fewer carbon atoms, such as a phenyl group or a benzyl group. That is, preferred specific examples of carbonate compounds include diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, ditrile 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 mentioned above can be synthesized using known methods, or commercially available compounds may be used.

[0050] [(III-1) Aromatic Diol Compounds] The aromatic diol compounds used in the polymerization process are used to constitute the main chain of the polycarbonate copolymer, as shown in the above formulas (A) and (B) which outline the polymerization reaction. Therefore, as aromatic diol compounds used in the polymerization process, monomers that can be used as materials for polycarbonate resins are preferred, for example, 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 Nylethane, 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) 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 include cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), 9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl)fluorene (BNEF), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, and 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-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 alicyclic diol compounds used in polymerization processes include the following: That is, isosorbide represented by the following formula (a compound in formulas (1-3) above where 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 in the formula below), etc., represented by the following formula; [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] Tricyclodecanedimethanol (TCDDM), represented by the following formula; [ka] Adamantane dimethanol such as 1,3-adamantanedimethanol represented by the following formula: [ka] And so on. In the main chain of the polycarbonate copolymer, it is preferable that the constituent units derived from these alicyclic diols are included.

[0052] The polycarbonate copolymer described above has high fluidity and is suitable for forming molded articles, and is preferably used in the molding of thin sheets, films, and the like.

[0053] [(IV) Transesterification catalysts] As a transesterification catalyst used in the polymerization process, a catalyst containing a basic compound is preferred. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Such compounds include organic salts of alkali metals and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, or alkoxides. Alternatively, quaternary ammonium hydroxides and their salts, amines, etc., can be used as basic compound catalysts. Furthermore, these compounds can be used individually or in combination of several types. The transesterification catalyst is more preferably one that contains an alkali metal carbonate or alkali metal hydroxide among the basic compound catalysts mentioned above. Specific examples of more preferred transesterification catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. The transesterification catalysts mentioned above can be prepared by known methods, or commercially available ones may 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 under reduced pressure in the molten state, by-products such as alcohols derived from the carbonate compound, such as aryl alcohols, are removed. By setting the reaction conditions in this way, the polymerization reaction can be carried out efficiently.

[0055] In the polymerization process, it is preferable to carry out the polymerization reaction under a pressure of 400 Pa or less. That is, the pressure in the polymerization reaction is preferably within the range of 400 Pa or less. In the polymerization process, it is preferable to maintain atmospheric pressure, or a state with minimal pressure reduction, for a certain period of time without reducing the pressure, and then further reduce the pressure within the system to advance the polymerization reaction. For example, in the polymerization process, 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 reduction process, in which the pressure within the reaction system is reduced in stages and the degree of reduction is increased midway through, is preferable because it allows for efficient removal of by-products such as alcohol while suppressing the distillation of raw materials.

[0056] The time required for the polymerization process is determined appropriately, taking into account the type of polycarbonate copolymer to be produced, pressure, temperature, and other conditions. For example, the total time required for the polymerization process is within 5 to 10 hours. More specifically, the reaction time before reduced pressure in the reaction system is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after reduced pressure is 1 to 5 hours, preferably 2 to 4 hours.

[0057] In the polymerization process, the temperature of the polymerization reaction described above is preferably in the range of 150 to 300°C. More preferably, the temperature of the polymerization reaction is 180 to 290°C, and even more preferably, 200 to 280°C.

[0058] Furthermore, the silane compounds, diaryl carbonates, and aromatic diol compounds mentioned above exhibit good compatibility with each other, allowing for the production of polycarbonate copolymers without the use of solvents in the polymerization process. This simplifies the polymerization process.

[0059] In the polymerization process, 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 molar amount of transesterification catalyst / molar amount of aromatic diol compound) is 1.0 × 10⁻⁶ -7 ~1.0×10 -2 (mol / mol: 0.1 to 10000 μmol / mol, or 1.0 × 10⁻⁶ -4 It is preferable that the molar ratio is ~10 mmol / mol. The above molar ratio is more preferably 1.0 × 10 -7 ~2.0×10 -5 It is mol / mol (or 0.5 to 20 μmol / mol).

[0060] In the polymerization process, 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 between 0.9 and 1.25, and more preferably between 0.95 and 1.2. Furthermore, in the polymerization process, the molar ratio of the aromatic diol compound to the total number of moles of diaryl carbonate and silane compound (i.e., the value of (total number of moles of diaryl carbonate and silane compound) / number of moles of 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) Constituent Units] The polycarbonate copolymer produced by the present invention is a polymer having siloxane structural units as described above, and specifically includes the following. In other words, a polycarbonate copolymer is a polymer having at least one siloxane structural unit represented by any of the following formulas (1-1) to (1-4) and a polycarbonate structural unit, which will be described in detail later. [ka] R in equations (1-1) to (1-4) 1 and R 2 The siloxane structure containing the above-mentioned diaryloxysilane compounds, dialkyldialkoxysilanes, or silicon compounds (siloxane compounds) is introduced.

[0062] In equations (1-1) to (1-4), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, which may have substituents. R 1 and R 2 However, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2. Also, R 1 and R 2 However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

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

[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 substituents, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In equations (1-1) to (1-3), J1 and K1 each independently represent integers between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2. In equation (1-3), A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, and L1 and L2 are preferably 1 or 2. In equations (1-1) and (1-2), X is independently either a single bond or one of the structural formulas represented by equation (2) below. [ka] In formula (2), R 11 , and R 12Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). R 11 , and R 12 Preferably, each is independently a hydrogen atom, a C1-C10 alkyl group which may have substituents, or a C6-C16 aryl group which may have substituents. In formula (2), a and b are each independently integers of 0 or 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. Furthermore, in the siloxane constituent unit, X is R 11 and R 12 It is preferable that the structure is a fluorene ring structure formed by the bonding of these elements together.

[0065] Furthermore, it is preferable that the siloxane constituent units include at least those represented by the following formula (1). [ka]

[0066] R in equation (1) 1 and R 2 The siloxane structure containing the above-mentioned diaryloxysilane compound, diarykoxysilane compound, or silicon compound (siloxane compound) is introduced. In equation (1), R 1 and R 2 Each of these independently represents an alkyl group, alkenyl group, or aryl group which may have substituents. 1 and R 2Each of these is an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents, or an aryl group having a total of 6 to 30 carbon atoms. R 1 and R 2 For preferred options, see R in the above equations (1-1) to (1-4). 1 and R 2 It is similar to that.

[0067] The above R 1 and R 2 Examples of substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups. R in equation (1) 1 and R 2 Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0068] In equation (1), R 3 ~R 10 For preferred options, see R in the above equations (1-1) to (1-4). 3 ~R 10 It is similar to that. The above R 3 ~R 10 Examples of substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups.

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

[0070] The polycarbonate constituent units of a polycarbonate copolymer can be represented by 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 of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. R 13 ~R 20 and R 40 ~R 51 However, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2. R 13 ~R 20 and R 40 ~R 51 However, if it is an alkenyl group which may have substituents, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. Also, R 13 ~R 20 and R 40 ~R 51 However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0072] In formulas (3-1) to (3-3), Z3 and Z4 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents, preferably alkylene groups having 1 to 3 carbon atoms, and more preferably alkylene groups having 1 or 2 carbon atoms. In equations (3-1) to (3-3), J2 and K2 each independently represent integers between 0 and 5, preferably between 0 and 3, and more preferably between 1 and 2. In equation (3-3), A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, and preferably L1 and L2 are between 0 and 2. In equations (3-1) and (3-2), Y is independently either a single bond or one of the structural formulas represented by equation (4). [ka] (In the formula, R 21 , and R 22 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 21 and R 22 The terms c and d represent a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these elements. Each of c and d independently represents an integer between 0 and 5000, or between 1 and 5000. R 21 , and R 22 Preferably, each is independently a hydrogen atom, a C1-C10 alkyl group which may have substituents, or a C6-C16 aryl group which may have substituents. In formula (4), c and d are each independently integers of 0 or between 1 and 5000, 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. Furthermore, in the polycarbonate boat structural units, Y is R 11 and R 12 It is preferable that the structure is a fluorene ring structure formed by the bonding of these elements together.

[0073] The polycarbonate constituent units preferably include at least those represented by the following formula (3). [ka]

[0074] In equation (3), R 13 ~R 20 For preferred options, see R in the above equations (3-1) to (3-2). 3 ~R 10 It is similar to that. The above R 13~R 20 Examples of substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups.

[0075] In equation (3), Y is the same as Y in equations (3-1) to (3-2) above.

[0076] [(II) Properties of polycarbonate copolymers] 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. Furthermore, the number of moles of polycarbonate constituent units is preferably 1 to 1000. These mole numbers represent the number of constituent units contained in one molecule of the polycarbonate copolymer, more preferably 10 to 800, and even more preferably 100 to 600.

[0078] In polycarbonate copolymers, the proportion of siloxane constituent units to the total number of moles of siloxane constituent units and polycarbonate constituent units is preferably 2.0% or more and 90% or less. The proportion of siloxane constituent units is more preferably 3.0% or more, for example, higher 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 polycarbonate copolymers are not used alone but as a mixture with other resins, it may be beneficial to significantly increase the proportion of the siloxane structural units mentioned above. For example, polycarbonate copolymers with a high Si content and a proportion of siloxane structural units of 30% or more, 50% or more, or 70% or more can achieve superior performance, such as high impact resistance and fluidity, by mixing them with polymers that do not contain Si or siloxane structural units, as will be described in detail later. Moreover, when applications where increasing the proportion of siloxane structural units is preferable, the upper limit of the proportion of siloxane structural units is not limited to 90%, but may be, for example, 92%, 95%, 98%, etc.

[0079] In polycarbonate copolymers, the molar ratio of siloxane constituent units to polycarbonate constituent units (i.e., the ratio of moles of siloxane constituent units to moles of polycarbonate constituent units) is preferably 0.01:99.99 to 99.99:0.01. The above molar ratio is more preferably 30:70 to 99.9:0.01, but other ranges, such as 1:99 to 99:1 or 10:90 to 90:10, are also acceptable.

[0080] In polycarbonate copolymers, the Q value (molten 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 It is preferable that the Q value is 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] In polycarbonate copolymers, the glass transition temperature (Tg) according to JIS K 7121 is preferably 40 to 200°C, more preferably 45 to 180°C, and more preferably 50 to 160°C.

[0082] In the polycarbonate copolymers described above, that is, polycarbonate copolymers having siloxane structural units represented by any of formulas (1-1) to (1-4) and polycarbonate structural units represented by any of formulas (3-1) to (3-4), it is preferable that the low molecular weight compounds with a weight-average molecular weight of 1,000 or less constitute 30% by weight or less, more preferably 20% by weight or less, 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 with 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 manufacture discs or complex and thin-walled products. In this regard, in polycarbonate copolymers, if the amount of low molecular weight compounds with a weight-average molecular weight of 1,000 or less is less than 1.5% by mass, mold contamination can be effectively prevented. Furthermore, while not particularly important, the lower limit of the content of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in polycarbonate copolymers is approximately 0.7% by weight. However, even if the content of the above low molecular weight compounds is 0.001% by weight, 0.01% by weight, or 0.1% by weight or more, there are no problems with the properties of the polycarbonate copolymer, especially when used in optical applications, and an effect of improved fluidity has also been confirmed. For this reason, the lower limit of the content of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in polycarbonate copolymers may be 0.001% by weight, 0.01% by weight, or 0.1% by weight.

[0083] The content of the low molecular weight compounds in the polycarbonate copolymer is calculated by summing the content of several types of low molecular weight compounds, which are impurities, from the ratio of the peak areas of each component obtained by GPC analysis, as will be described in detail in the examples below. In other words, as will be described in detail below, the proportion of low molecular weight compounds with a molecular weight of 1,000 or less in the polycarbonate copolymer is calculated from the ratio of the area from 20.5 min to 21.5 min to the area from 0 min to 21.5 min under predetermined GPC analysis conditions.

[0084] In the above-mentioned polycarbonate copolymer, that is, a polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), the total content of the cyclic compounds represented by the following formulas (5-1) to (5-3) is preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less, based on the total weight of the polycarbonate copolymer. If the content of these cyclic dimers is within the above-mentioned range, the properties of the polycarbonate copolymer, especially when used in optical applications, can be said to be acceptable. [ka] In equations (5-1) to (5-3), m and n represent the total number of constituent units containing the (-OSi(R1R2)O-) moiety and the total number of constituent units containing the (-OC(=O)O-) moiety in each annular body. That is, in the annular body of equation (5-1), if constituent units other than those containing the (-OSi(R1R2)O-) moiety are included, and in the annular body of equation (5-2), if constituent units other than those containing the (-OC(=O)O-) moiety are included, then m and n represent the total number of constituent units in the annular body shown in the equation, respectively. In particular, equation (5-3) includes annular bodies in which constituent units containing the (-OSi(R1R2)O-) moiety and constituent units containing the (-OC(=O)O-) moiety are mixed, for example, when they are arranged alternately. In this case as well, m and n represent the total number of constituent units in the annular body shown in the equation, respectively. In formula (5-1), m represents an integer from 2 to 10, preferably from 2 to 5, more preferably 2 or 3, and even more preferably 2. In formula (5-2), n represents an integer from 2 to 10, preferably from 2 to 5, more preferably 2 or 3, and even more preferably 2. In equation (5-3), the sum of the values ​​of m is between 1 and 10, and the sum of the values ​​of n is between 1 and 10. Furthermore, m and n are preferably between 1 and 5, more preferably 1 or 2, and even more preferably 1. In equation (5-3), as mentioned above, the arrangement of the constituent units containing the (-OSi(R1R2)O-) moiety and the constituent units containing the (-OC(=O)O-) moiety in the ring body of equation (5-3) is arbitrary. In formulas (5-1) to (5-3), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, which may have substituents, 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 between 0 and 5, preferably between 0 and 3, and more preferably between 1 and 2. Also, in equations (5-1) to (5-3), R 1 , R 2 , R 3~R 10 , R 13 ~R 20 And X is R in equations (1-1) and (1-2). 1 , R 2 , R 3 ~R 10 , R 13 ~R 20 The same applies to X, respectively.

[0085] Furthermore, specific examples of compounds of formulas (5-1) to (5-3) include the cyclic compounds of formulas (5-1') to (5-3') shown below. [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=1 to 3, n=1 to 3, preferably both 1 or 2, more preferably both 1.

[0086] Furthermore, the polycarbonate copolymer may 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 resulting from side reactions of the polymerization reaction for the production of 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 equations (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 equations (1-1) and (1-2). In equations (6-1) and (6-2), X1 and X2 are each independently C1-C5 alkylene groups which may have substituents, preferably C1-C3 alkylene groups, and more preferably C1 or C2 alkylene groups. i and ii each independently represent an integer between 0 and 5, preferably between 0 and 3, and more preferably between 1 and 2. n represents an integer between 2 and 10, preferably between 2 and 5, and more preferably 2 or 3, for example, 2.

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

[0088] Furthermore, specific examples of compounds of formula (6-1) and (6-2) include the cyclic compounds of formula (6-1') and (6-2') shown below. [ka] Furthermore, in equations (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 polycarbonate copolymers, 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 polycarbonate copolymers, the ratio of the total weight of silicon atoms (total Si amount) based on the total weight of the polycarbonate copolymer is preferably 0.1 to 20% by mass, more preferably 1.0 to 15% by mass, even more preferably 2.0 to 12% by mass, and particularly preferably 3.0 to 10% by mass (for example, 3.1% by mass or more, or more than 3.1% by mass and 9.8% by mass or less).

[0091] Next, the compositions according to the present invention, namely compositions containing the polycarbonate copolymer and the like described above, will be described in detail.

[0092] <3. Composition> The composition of the present invention comprises the polycarbonate copolymer described above and a polycarbonate resin that does not fall under the category of the polycarbonate copolymer described above. Examples of polycarbonate resins that do not fall under the category of the polycarbonate copolymer described above include polycarbonate resins that do not contain a siloxane structure at all or substantially.

[0093] The types of polycarbonate resins that do not fall under the above-mentioned polycarbonate copolymers are not particularly limited as long as they contain a -[OR-OCO]- unit (where R is an aliphatic group, an aromatic group, or both an aliphatic and an aromatic group, and furthermore, they have a linear or branched structure) containing a carbonate ester bond in the molecular main chain. Furthermore, polycarbonate resins that do not fall under the above-mentioned polycarbonate copolymers may also contain polyester carbonate. Similarly, the polyester carbonate is not particularly limited as long as it contains a -[OR-OC]- unit (where R is as described above) containing a carbonate ester 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 also contain resins other than polycarbonate resin, preferably thermoplastic resins. The type of thermoplastic resin is not particularly limited, but in addition to polycarbonate resin and polyester carbonate resin, examples of various resins include acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyethersulfone, cellophane, and aromatic polyamides.

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

[0097] Compositions with excellent properties can be produced using polycarbonate copolymers with a high Si content. By mixing a polycarbonate copolymer with a Si content of, for example, 0.1% by mass or more, with a resin that substantially does not contain siloxane structural units, preferably a polycarbonate resin, the resulting composition can achieve both excellent impact resistance and fluidity.

[0098] Furthermore, compositions containing polycarbonate copolymers may include phenolic compounds that may be produced as by-products of the polymerization reaction, as well as silane compounds, carbonate compounds, and diol compounds that remain unreacted. Since phenolic compounds and DPC, which are impurities, can cause a decrease in the strength of molded articles and the generation of odors, it is preferable to keep their content as low as possible. For this reason, the content of phenolic compounds, silane compounds, carbonate compounds, and diol compounds may be reduced to the point of being undetectable, but from the viewpoint of productivity, they may be included in the composition to the extent that the effect is not impaired. In addition, by including a predetermined amount of monomer residue, for example, 1 to 1000 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 good plasticity can be obtained when the resin melts.

[0099] Next, a molded article according to the present invention, which includes 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 a polycarbonate copolymer, etc. The molding method for the molded article is not particularly limited, and examples of molded articles include injection molded articles, press molded articles, blow molded articles, extruded articles, vacuum molded articles, and pressure molded articles.

[0100] Furthermore, the optical lens according to the present invention is 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 a range suitable for use as a lens.

[0101] [II. Polysiloxane Compounds] The methods for producing polysiloxane compounds such as polyarylenesiloxane in the present invention all involve a polymerization step in which an oxysilane compound, such as a predetermined diaryloxysilane compound, and a diol compound, such as an aromatic diol compound, are polymerized in the presence of a transesterification catalyst, as will be described in detail later. The methods for producing polysiloxane compounds will be described below. Furthermore, in the method for producing polysiloxane compounds, the raw materials, reaction conditions, etc. described for the polycarbonate copolymer described above may also be used, and in the method for producing polycarbonate copolymer described above, the raw materials, reaction conditions, etc. described for the method for producing polysiloxane compounds described below may also be used.

[0102] The polymerization reaction described above can be schematically shown below. For example, when a diphenoxysilane compound (Si(CH3)2(OPh)2), 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. In other words, a polyarylenesiloxane compound having a siloxane structure is produced by the reaction of formula (A) below. In this polymerization reaction, aryl alcohols such as phenol (PhOH) are produced as by-products, as described below. Therefore, in the polymerization process, the polymerization reaction proceeds under reduced pressure while the mixture of the above-mentioned components is molten, and the by-products, such as aryl alcohols like phenol, are removed. [ka] The method for producing polysiloxane compounds according to the present invention will be described in detail below. Note that the polysiloxane compounds include polyarylenesiloxane compounds, polyalkylenesiloxane compounds, mixtures thereof, and forms in which the polymer chain contains both constituent units derived from diaryloxysilane compounds and constituent units derived from diarykoxysilane compounds, which will be described in detail later.

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

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

[0105] Diaryloxysilane compounds are classified under the general formula Si(R a R b When expressed as (OAr)², R a and R b Each of these is independently selected from alkyl groups and aryl groups. a and R b Each of these is preferably independently either an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents, or an aryl group having a total of 6 to 30 carbon atoms. More preferably, R a and R bHowever, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2. Also, R a and R b However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0106] Examples of the substituents mentioned above include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups. R in equation (1) a and R b Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

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

[0108] Specific examples of dialkyldiaryloxysilanes include dimethyldiphenoxysilane, methylethyldiphenoxysilane, and diethyldiphenoxysilane, while specific examples of diaryldiaryloxysilanes include diphenyldiphenoxysilane. Furthermore, specific examples of monoalkylmonaryldiaryloxysilanes include methylphenylphenoxysilane. These diaryloxysilane compounds can be synthesized using known methods, or commercially available compounds may be used.

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

[0110] Dialkoxysilane compounds are classified under the general formula Si(R a R b )(OR C When expressed as )², R a and R b Each of these independently corresponds to the R listed in the column for (A-1) diaryloxysilane compounds. a and R b The same alkyl and aryl groups are selected. Furthermore, as is clear from formula (A) above, the alkoxy group (OR) of the silane compound C The alkoxy group is not introduced into the polymer chain of the polycarbonate copolymer, but rather generates by-products such as methanol (MeOH). For this reason, the type of alkoxy group is not particularly limited. However, in order to remove by-products from the reaction system as easily as possible during the polymerization process, the 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. Furthermore, specific examples of monoalkylmonoaryldialkoxysilanes include methylphenyldimethoxysilane.

[0112] [(II) Diol Compounds] Examples of diol compounds used in the production of polysiloxane compounds include aromatic diol compounds and alicyclic diol compounds. A mixture of aromatic diol compounds and alicyclic diol compounds may also be used as the diol compound.

[0113] (A-1) Aromatic diol compounds The aromatic diol compounds used in the polymerization process are used to constitute the main chain of polysiloxane compounds such as polyarylenesiloxane compounds, as shown in formula (A) above, which outlines the polymerization reaction. Therefore, as aromatic diol compounds used in the polymerization process, monomers that can be used as materials for polycarbonate resins are preferred, for example, 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 Nylethane, 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) 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 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 above section [(III-1) Aromatic Diol Compounds] relating to polycarbonate copolymers can also be used in the polymerization process for the production of polysiloxane compounds.

[0114] (A-2) Alicyclic diol compounds Alicyclic diol compounds used in the polymerization process are also used to constitute the main chain of polysiloxane compounds. Specific examples of alicyclic diol compounds include spiroglycols, cyclohexanedimethanol, PCPDM, and TCDDM. In addition, the alicyclic diol compounds described in the above section [(III-2) Alicyclic Diol Compounds] relating to polycarbonate copolymers can also be used in the polymerization process for the production of polysiloxane compounds.

[0115] [(III) Transesterification catalyst] As a transesterification catalyst used in the polymerization process, a catalyst containing a basic compound is preferred. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Such compounds include organic salts of alkali metals and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, or alkoxides. Alternatively, quaternary ammonium hydroxides and their salts, amines, etc., can be used as basic compound catalysts. Furthermore, these compounds can be used individually or in combination of several types. The transesterification catalyst is more preferably one that contains an alkali metal carbonate or alkali metal hydroxide among the basic compound catalysts mentioned above. Specific examples of more preferred transesterification catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. Transesterification catalysts can be prepared by known methods, or commercially available ones may 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-products, aryl alcohol and / or alkyl alcohol, are removed under reduced pressure in the molten state. By setting the reaction conditions in this way, the polymerization reaction can be carried out efficiently.

[0117] In the polymerization process, the pressure in the polymerization reaction described above is preferably within the range of 101,300 Pa or less. More preferably, the pressure in the polymerization reaction is 27,000 Pa or less, and even more preferably, 400 Pa or less. In the polymerization process, it is preferable to maintain atmospheric pressure, or a state with minimal pressure reduction, for a certain period of time without reducing the pressure, and then gradually reduce the pressure within the system to further advance the polymerization reaction. By gradually increasing the degree of pressure within the reaction system in this way, the necessary work at the start of the reaction can be started under atmospheric pressure, and by-products such as aryl alcohols or alkyl alcohols can be easily removed from the reaction system. Specifically, it is preferable to proceed with the reduction process at a pace 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 always necessary to carry out the polymerization reaction under reduced pressure in the polymerization process. It is preferable to reduce the pressure in the reaction system after the polymerization reaction has progressed to a certain extent, preferably from a state in which the raw materials are molten. For example, as will be described later, it is preferable to gradually increase the reaction temperature in the polymerization process. Therefore, it is preferable to start the reduced pressure process after the temperature of the reaction system has risen to a certain extent, for example, to 150°C or higher, more preferably to 180°C or higher.

[0119] In the polymerization process, the temperature of the polymerization reaction described above is preferably in the range of 150 to 300°C. More preferably, the polymerization reaction temperature is 180 to 290°C, and even more preferably 200 to 280°C. Thus, in the polymerization process, 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. Furthermore, it is preferable to carry out the polymerization process under reduced pressure. Furthermore, in order to gradually generate and remove by-products such as aryl alcohols or alkyl alcohols, it is preferable to gradually raise the temperature from room temperature to, for example, the reaction temperature set within the range described above. The temperature increase is preferably carried out at a pace of about 1 to 10°C / min, more preferably at 2 to 8°C / min, and even more preferably at 3 to 7°C / min.

[0120] The time required for the polymerization process is determined appropriately, taking into consideration the type of polysiloxane compound to be used, the pressure, temperature, and other reaction conditions. For example, the total time required for the polymerization process is within 1 to 10 hours. More specifically, the reaction time before the aforementioned 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 components have good compatibility with each other, and polycarbonate copolymers can be produced without using solvents in the polymerization process. Thus, since solvents such as halogenated solvents are not required, it is possible to reduce the environmental burden of the polymerization reaction and simplify the polymerization process.

[0122] Furthermore, the by-products generated in the polymerization process are the aforementioned aryl alcohols, alkyl alcohols, etc., which are easily removed from the reaction system and do not require special treatment for safety reasons. For this reason, the method for producing polysiloxane compounds according to the present invention can reduce the environmental burden compared to conventional methods that produce or use acids as by-products.

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

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

[0125] Next, the polysiloxane compounds according to the present invention will be described in detail. [(V) Polysiloxane compounds] The polysiloxane compounds produced by the present invention are polymers having siloxane structural units as described above, and specifically include the following. In other words, a polyarylenesiloxane compound is a polymer having at least one siloxane structural unit represented by one of the following formulas (1-1') to (1-4'). [ka]

[0126] In equations (1-1') to (1-4'), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, which may have substituents. R 1 and R 2 However, if the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2. Also, R 1 and R 2However, if the aryl group may have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

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

[0128] In formulas (1-1') to (1-3'), Z1 is independently a C1 to C5 alkylene group which may have substituents, preferably a C1 to C3 alkylene group, and more preferably a C1 or C2 alkylene group. In equations (1-1') to (1-3'), J1 and K1 each independently represent integers between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2. In equation (1-3'), A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, and L1 and L2 are preferably 1 or 2. In equations (1-1') and (1-2'), X is independently either a single bond or one of the structural formulas represented by equation (2) below. [ka] In formula (2), R 11 , and R 12 Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R 11 and R 12 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). R 11 , and R 12 Preferably, each is independently a hydrogen atom, a C1-C10 alkyl group which may have substituents, or a C6-C16 aryl group which may have substituents. In formula (2), a and b are each independently integers of 0 or 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. Furthermore, in the siloxane constituent unit, X is R 11 and R 12 It is preferable that the structure is a fluorene ring structure formed by the bonding of these elements together.

[0129] Furthermore, it is preferable that the siloxane constituent units include at least those represented by the following formula (1'). [ka]

[0130] R in equation (1') 1 and R2 The siloxane structure containing is introduced from the oxysilane compound mentioned above. In equation (1'), R 1 and R 2 For preferred options, see R in the above equations (1-1')~(1-4'). 1 and R 2 It is similar to that.

[0131] The above R 1 and R 2 Examples of substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups. R in equation (1') 1 and R 2 Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0132] In equation (1'), R 3 ~R 10 For preferred options, see R in the above equations (1-1')~(1-4'). 1 and R 2 It is similar to that. The above R 3 ~R 10 Examples of substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, and mercapto groups.

[0133] In equation (1'), m represents an integer between 10 and 1,000. The value of m in equation (1') is preferably between 20 and 800, and more preferably between 30 and 500.

[0134] In equation (1), X is R in equations (1-1') and (1-2') above. 1 and R 2 It is similar to that.

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

[0136] For polysiloxane compounds such as polyarylenesiloxane compounds, the glass transition temperature (Tg) in accordance with JIS K 7121 is preferably 40 to 200°C, and more preferably 45 to 160°C.

[0137] In the above-mentioned polysiloxane compounds, that is, polysiloxane compounds having siloxane structural units represented by any of formulas (1-1) to (1-4) and formulas (1-1') to (1-4'), the weight-average molecular weight is preferably 5,000 to 300,000, and the total content of the cyclic product represented by the following formula (5-4) is preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less, based on the total weight of the polysiloxane compound. If the total content of these small molecular weight cyclic compounds, such as cyclic dimers, is within the range described above, the properties of the polysiloxane compound, especially when used in optical applications, can be considered good. [ka] In formula (5-4), the arrangement of the constituent units represented by formula (5-4) with other constituent units is arbitrary. That is, constituent units other than those explicitly represented in formula (5-4) may be included, but in any case, the sum of the values ​​of m is between 2 and 10, preferably between 2 and 5, more preferably 2 or 3, for example 2. R 1 , R 2 , R 3 ~R10 And X is the same as in equations (1-1) and (1-2). In formula (5-4), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, which may have substituents, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In equation (5-4), i and ii each independently represent integers between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2.

[0138] The lower limit for the content of cyclic compounds with low molecular weight in polysiloxane compounds is approximately 0.7% by weight, although this is not particularly important, similar to the content of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in polycarbonate copolymers. However, even if the content of the above low molecular weight compounds is 0.001% by weight, 0.01% by weight, or 0.1% by weight or more, there are no problems with the properties of the polysiloxane compound, especially when used in optical applications, and the fluidity may improve. For this reason, the lower limit for the content of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in polysiloxane compounds may be 0.001% by weight, 0.01% by weight, or 0.1% by weight.

[0139] The content of the low molecular weight cyclic compounds in the polysiloxane compound is calculated by summing the content of several types of low molecular weight compounds, which are impurities, from the ratio of the peak areas of each component obtained by GPC analysis, as will be described in detail in the examples below. In other words, as will be described in detail below, it can be calculated from a predetermined GPC area ratio, similar to the measurement of the proportion of low molecular weight compounds with a molecular weight of 1,000 or less in polycarbonate copolymers.

[0140] Furthermore, among the cyclic compounds represented by formula (5-4), the cyclic dimer shown in formula (5-4') can be cited as a specific example. The molecular structure of the cyclic dimer of formula (5-4') and the fact that such cyclic dimers can be included in polysiloxane compounds have been confirmed. [ka]

[0141] Furthermore, the polysiloxane compound may 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 resulting from side reactions of the polymerization reaction for the production of the polysiloxane compound. The content of these cyclic dimers in the polysiloxane compound 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 polysiloxane compound. [ka] In equations (6-1) and (6-2), the arrangement of the constituent units represented by these equations with other constituent units is arbitrary. That is, constituent units other than those explicitly represented in equations (6-1) and (6-2) may be included, but in either case, the sum of the values ​​of n is between 2 and 10, preferably between 2 and 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 substituents, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. In equations (6-1) and (6-2), i and ii each independently represent an integer between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2. Furthermore, in equations (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] Furthermore, the lower limit of the total content of cyclic dimers represented by formulas (6-1) and (6-2) in the polysiloxane compound is not particularly limited, but may be, for example, 0.001% by weight, 0.01% by weight, or 0.1% by weight. The presence of a small amount of cyclic dimers may contribute to improving the fluidity of the polysiloxane compound during molding.

[0143] Furthermore, specific examples of compounds of formula (6-1) and (6-2) include the cyclic compounds of formula (6-1') and (6-2') shown below. [ka] Furthermore, in equations (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] In the case of polysiloxane compounds, 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.

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

[0146] Next, the compositions according to the present invention, that is, compositions containing the polysiloxane compounds and the like described above, will be described in detail.

[0147] <3. Composition> The composition of the present invention comprises the above-mentioned polysiloxane compound and a polycarbonate resin. Examples of the polycarbonate resin include a polycarbonate resin that is completely or substantially free of siloxane structures.

[0148] The type of polycarbonate resin included in the composition along with the polysiloxane compound described above is not particularly limited, as long as it contains a -[OR-OCO]- unit (where R is an aliphatic group, an aromatic group, or both an aliphatic and an aromatic group, and furthermore, it may have a linear or branched structure) containing a carbonate ester bond in its molecular backbone. Furthermore, the polycarbonate resin that does not fall under the polysiloxane compound described above may include polyester carbonate. Similarly, the polyester carbonate is not particularly limited, as long as it contains a -[OR-OC]- unit (where R is as described above) containing a carbonate ester bond in its molecular backbone.

[0149] The weight-average molecular weight of the polycarbonate resin included 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 also contain resins other than polycarbonate resin, preferably thermoplastic resins. The type of thermoplastic resin is not particularly limited, but in addition to polycarbonate resin and polyester carbonate resin, examples of various resins include acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyethersulfone, cellophane, and aromatic polyamides.

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

[0152] Compositions with excellent properties can be produced using polysiloxane compounds with a high Si content. By mixing a polysiloxane compound with a Si content of, for example, 0.1% by mass or more with a resin that substantially does not contain siloxane structural units, preferably a polycarbonate resin, the resulting composition can achieve both excellent impact resistance and fluidity.

[0153] Furthermore, compositions containing polysiloxane compounds may include phenolic compounds that may be produced as by-products of the polymerization reaction, as well as oxysilane and diol compounds that remain unreacted. Since phenolic compounds and DPC, which are impurities, can cause a decrease in the strength of the molded article and the generation of odors, it is preferable to keep their content as low as possible. For this reason, the content of phenolic compounds, oxysilane compounds, and diol compounds may be reduced to the point of being undetectable, but from the viewpoint of productivity, they may be included in the composition to the extent that the effect is not impaired. In addition, by including a predetermined amount of monomer residue, for example, 1 to 1000 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 good plasticity can be obtained when the resin melts.

[0154] <4. Molded body> Next, we will describe molded articles containing polysiloxane compounds such as the polyarylenesiloxane compounds mentioned above. The molded articles of the present invention are obtained by molding polysiloxane compounds such as the polyarylenesiloxane compounds described above. The molding method for the molded articles is not particularly limited, and examples of molded articles include injection molded articles, press molded articles, blow molded articles, extruded articles, vacuum molded articles, and pressure molded articles.

[0155] Furthermore, 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 in optical films, optical lenses, and the like. In addition, the optical lens of the present invention has a refractive index, Abbe number, etc., within a range suitable for use as a lens.

[0156] (Regarding secondary components) Inactivator In the polycarbonate copolymer and polysiloxane compound of the present invention, the catalyst may be removed or deactivated after the polymerization reaction is complete in order to maintain thermal stability and hydrolysis stability. A known method of deactivating the catalyst by adding an acidic substance can be suitably carried out. Specifically, the acidic substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as p-toluenesulfonate butyl and p-toluenesulfonate hexyl; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphorous acid esters such as triphenyl phosphate, monophenyl phosphate, diphenyl phosphate, diethyl phosphate, di-n-propyl phosphate, di-n-butyl phosphate, di-n-hexyl phosphate, dioctyl phosphate, and monooctyl phosphate; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, and dioctyl phosphate. Phosphate esters such as monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearate chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride are preferably used. These deactivators may be used, for example, in amounts of 0.001 to 50 moles, preferably 0.01 to 30 moles, relative to the amount of catalyst.

[0157] additives <Stabilizer> Stabilizers may be added to the polycarbonate copolymer and polysiloxane compound of the present invention. Examples of stabilizers include heat stabilizers and antioxidants. When a stabilizer is added, the amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.02 parts by mass or more, and also 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, per 100 parts by mass of the polycarbonate copolymer or polysiloxane compound. Only one type of stabilizer may be included, or two or more types may be included. When two or more types are included, it is preferable that the total amount is within the above range.

[0158] <<Heat stabilizer>> Examples of heat stabilizers include phenolic, phosphorus-based, and sulfur-based heat stabilizers. Specifically, these include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphate; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; and organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds. In addition, at least one selected from the group consisting of phosphorous acid ester compounds (a), phosphorous acid (b), and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite (c), in which at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group with 1 to 25 carbon atoms, can be mentioned.Specific examples of phosphite compounds (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, monobutyldiphenyl phosphite, monodecyldiphenyl phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol Examples include diphenyl phosphite, 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 individually or in combination of two or more. Examples of organic phosphite compounds include "Adeka Stab 1178 (trade name, same below)", "Adeka Stab 2112", and "Adeka Stab HP-10" from Adeka Corporation, "JP-351", "JP-360", and "JP-3CP" from Johoku Chemical Industry Co., Ltd., and "Irgaphos 168" from BASF. Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate. The proportion of heat stabilizer to be added, when included, is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.03 parts by mass or more, and also preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate copolymer or polysiloxane compound. The heat stabilizer may contain only one type or two or more types. If two or more types are included, it is preferable that the total amount be within the above range.

[0159] <<Antioxidant>> Examples of antioxidants include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, and polyphenolic 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-ter [t-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], thiodiethylenebis[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]phosphoate, 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(oxy Examples include bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 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-triazine-2-ylamino)phenol, etc. Examples of phenolic antioxidants include BASF's "Irganox 1010" (registered trademark, hereinafter the same) and "Irganox 1076," and Adeka's "Adeka Stab AO-50" and "Adeka Stab AO-60." The proportion of antioxidant added, when included, is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate copolymer or polysiloxane compound. The antioxidant may contain only one type or two or more types. If two or more types are included, it is preferable that the total amount is within the above range.

[0160] The polycarbonate copolymer and polysiloxane compound of the present invention may contain various additives without departing from the spirit of the invention. Examples of additives include at least one additive selected from flame retardants, flame retardant enhancers, ultraviolet absorbers, mold release agents, and colorants, and it is preferable to include at least one of a flame retardant and a mold release agent. Furthermore, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc., may be added, provided that they do not significantly impair the desired physical properties.

[0161] <Flame retardant> The polycarbonate copolymers and polysiloxane compounds of the present invention may contain various additives, provided that the invention is not departing from the spirit of the present invention. Flame retardants such as organometallic salt flame retardants, phosphorus-based flame retardants, and silicone-based flame retardants may be included. 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 Japanese Patent Application Publication No. 2016-183422, the contents of which are incorporated herein by reference.

[0162] <UV absorber> Examples of UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide, as well as organic UV 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. Among these, benzotriazole-based and benzophenone-based organic UV absorbers are preferred.In particular, specific examples of benzotriazole compounds 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, and 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazole-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [2-yl]-5-(octyroxy)phenol, 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazine-4-one], [(4-methoxyphenyl)-methylene]-propanedionic 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)pheno Examples include 2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], and [methyl-3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate.Among the above, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazole2-yl)phenol] are preferred. Specific examples of benzophenone-based UV absorbers 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. Furthermore, specific examples of phenyl salicylate-based UV absorbers include phenyl salicylate and 4-tert-butyl-phenyl salicylate. In addition, specific examples of triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]phenol and 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-(octyloxy)phenol. Furthermore, specific examples of hindered amine-based UV absorbers include bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate. The proportion of UV absorber to be added is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 3 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of polycarbonate copolymer or polysiloxane compound. One type of UV absorber may be used, or two or more types may be used. If two or more types are used, it is preferable that the total amount be within the above range.

[0163] <Release agent> Examples of release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specifically, at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15000, and polysiloxane-based silicone oils can be mentioned. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferably aliphatic saturated monovalent 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, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those mentioned above can be used as the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid with an alcohol. On the other hand, saturated or unsaturated monohydric or polyhydric alcohols can be used as the alcohol. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, monohydric or polyhydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols with 30 or fewer carbon atoms are more preferred. Here, alicyclic compounds are also included in the term aliphatic. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. The above ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, and may also be mixtures of multiple compounds.Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly 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 with a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Here, alicyclic hydrocarbons are also included in aliphatic hydrocarbons. Furthermore, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxidized polyethylene wax are preferred, and paraffin wax and polyethylene wax are 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 is preferably 0.001 parts by mass or more, more preferably 0.01 parts 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. One type of release agent may be used, or two or more types may be used. If two or more types are used, it is preferable that the total amount be within the above range.

[0164] <Coloring agent> The coloring agent may be either a dye or a pigment, and examples include inorganic pigments, organic pigments, organic dyes, etc. Examples of inorganic pigments include sulfide-based pigments such as carbon black, cadmium red, and cadmium yellow; silicate-based pigments such as ultramarine; oxide-based pigments such as titanium dioxide, zinc oxide, 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; chromic acid-based pigments such as lead yellow and molybdate orange; and ferrocyanate-based pigments such as Prussian blue. Furthermore, examples of organic pigments and organic dyes used as colorants include phthalocyanine-based dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green (dyes or pigments are referred to as dyes and pigments, the same applies hereinafter); azo-based dyes and pigments such as nickel azo yellow; condensed polycyclic dyes and pigments such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; and quinoline, anthraquinone, heterocyclic, and methyl-based dyes and pigments. Among these, titanium dioxide, carbon black, cyanine, quinoline, anthraquinone, and phthalocyanine-based dyes and pigments are preferred in terms of thermal stability. Furthermore, for the purpose of improving handling properties during extrusion and improving dispersibility in the resin composition, colorants may also be used in the form of masterbatches with polystyrene resins, polycarbonate resins, or acrylic resins. The proportion of colorant added, when included, 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 also 0.1 parts by mass or more, per 100 parts by mass of polycarbonate copolymer or polysiloxane compound. Only one type of colorant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0165] Molded bodies other than lenses There are no restrictions on the shape, pattern, color, dimensions, etc., of molded articles obtained using polycarbonate copolymers or polysiloxane compounds; these can be arbitrarily set according to their intended use. Specific examples of molded articles include electrical and electronic equipment, office automation (OA) equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous items, lighting equipment parts, various household electrical appliance parts, housings, containers, covers, storage compartments, cases for electrical appliances, covers and cases for lighting fixtures, etc. Examples of electrical and electronic equipment include personal computers, game consoles, television receivers, display devices such as liquid crystal displays and plasma displays, printers, copiers, scanners, fax machines, electronic organizers and personal digital assistants (PDAs), electronic desktop calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, drives and readers for recording media, mice, numeric keypads, CD (Compact Disc) players, MD (MiniDisc) players, portable radios and audio players, etc. Other examples of molded products include illuminated signs, LCD backlights, lighting displays, traffic signs, signboards, screens, automotive parts (in-vehicle parts) such as reflectors and meter components, toys, and decorative items. The polycarbonate copolymers and polysiloxane compounds of this application exhibit excellent impact resistance and high fluidity during melting, and can be formed into molded articles with a fine structure, making them suitable for use as automotive electrical and electronic components, mechanical parts, and vehicle parts. Examples of such parts include automotive interior panels, automotive lamp lenses, automotive inner lenses, automotive lens protective covers, and automotive light guides.

[0166] Method for molding a molded body The method for manufacturing the molded article of the present invention is not particularly limited, and any molding method commonly used for resins such as polycarbonate resin can be arbitrarily employed. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using a heat-insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, and press molding. Furthermore, a molding method using a hot runner system can also be used.

[0167] Other resins The polycarbonate copolymer and polysiloxane compound of the present invention may optionally contain 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, for example, 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 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 include core / shell type elastomers such as composite (MAS) and polyester 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. [Examples]

[0168] [Examples of polycarbonate resin] <Measurement of weight-average molecular weight (Mw) in polystyrene equivalent> 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 of each peak were plotted from the measured standard polystyrene, and a cubic approximation was performed to obtain the 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 is the i-th division point when the molecular weight M is divided, W is the division point) i The i-th weight is M i represents the i-th molecular weight. Furthermore, the molecular weight M represents the molecular weight in polystyrene terms at the same elution time on the calibration curve. [Measurement conditions] • Equipment: Labsolutions manufactured by Shimadzu Corporation • 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 percentage 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 an 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 data obtained from GPC analysis under the above conditions. Specifically, GPC analysis was performed under the conditions described in the section on <Measurement of weight-average molecular weight (Mw) in polystyrene equivalent>, and the proportion of low molecular weight compounds (B / A × 100 (%)) was measured based on the ratio of the GPC area (A) of peaks with a retention time of 21.5 minutes or less, which is considered to correspond to the total amount of compounds contained in the polycarbonate resin sample, and the GPC area (B) of peaks observed 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)> As measurement samples, 5–12 mg test pieces were weighed into an AI autosampler sample container (RDC aluminum pan, 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. Measurements were performed using a differential scanning calorimeter (DSC) under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), with 10.0 mg of sapphire used as the reference cell. The sample, adjusted to 30°C, was heated to 280°C at a rate of 20°C / min, then cooled to 30°C at a rate of 20°C / min. After that, the sample was heated to 280°C at a rate of 10°C / min and measured. Measurement device: 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. 150 g of ethanol was added dropwise to the resin solution over 30 minutes while stirring. 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 make 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 and analyzed and quantified by GC / FID as a 1000 μg / mL solution. The quantitative values ​​are 2,2-bis(4-hydroxyphenyl)propane equivalent values ​​obtained from a pre-prepared calibration curve for 2,2-bis(4-hydroxyphenyl)propane. [GC / FID measurement conditions] • Equipment: Shimadzu Corporation GC2025 • Column: Capillary column DB-35, 30mm x 0.25mm x 0.25μm • Heating conditions: 40°C–300°C (hold for 5 minutes), 10°C / min • Injection port temperature: 300℃, injection volume: 1.0μL (split ratio 1:20) Carrier gas: He ·Air flow rate: 400mL / min ·H2 flow rate: 40mL / min Makeup gas: 30 mL / min • Standard substance: 2,2-bis(4-hydroxyphenyl)propane

[0172] <Measurement of cyclic dimers> The content of the aforementioned cyclic dimer 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. 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. Next, 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 stirring 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 B and precipitate B. Next, 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 stirring 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 obtained oligomer components A, B, and C were dissolved in dichloromethane to a 1000 μg / mL solution, and the cyclic dimers were analyzed by GC-Q-MS / FID. The quantitative values ​​were calculated as 2,2-bis(4-hydroxyphenyl)propane equivalents from a pre-prepared calibration curve for 2,2-bis(4-hydroxyphenyl)propane. [GC-Q-MS / FID measurement conditions] • Equipment: Agilent Technologies, Inc. Agilent-7890B / Agilent-5975C MSD Inert XL MSD with TAD • Column: DB-5MS, 15mm × 0.25mm × 0.1μm ·Restrictor(MS):0.18mm×1.44mm ·Restrictor(FID):0.18mm×0.53mm • Heating conditions: 50°C (hold for 2 minutes) - 320°C (hold for 15 minutes), 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 Makeup gas: 25 mL / min • Standard substance: 2,2-bis(4-hydroxyphenyl)propane • Determination of cyclic dimers: Determination based on peak intensity at 16.6 min.

[0173] <Liquidity (Q-value)> The melting flow volume per unit time (cm³) measured at 280℃ and a load of 160kg. -3 This represents the molten flow volume measured using a Shimadzu Corporation CFT-500D type nozzle (nozzle diameter 1 mm x nozzle length 10 mm), with the value per unit time calculated from a stroke of 7.0 to 10.0 mm.

[0174] <Charpy impact test> The Charpy impact strength (kJ / m²) of the molded test specimen was determined in accordance with JIS-K7111. 2 ) was measured.

[0175] <Method for measuring refractive index (nd)> Refractive index (nd): The refractive index was measured using an Abbe refractometer on a 3 mm thick right-angle piece made of the polycarbonate copolymer produced in the example, according to the method of JIS-K-7142. <Method for measuring Abbe number (νd)> For the 3 mm thick right-angle pieces made of polycarbonate resin manufactured in the examples, the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm were measured 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 using the method described in US2012 / 184702. 176.34 g (1.87 mol) of phenol was stirred at 50°C under an N2 atmosphere, and 113.24 g (0.88 mol) of dimethyldichlorosilane was added dropwise over 30 min. One hour after the end of addition, by-products were removed by distillation under reduced pressure at 170°C and 200 hPa. The reaction mixture 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 washed organic layer was extracted. After removing residual water with anhydrous magnesium sulfate, the oily component was obtained by distillation of dichloromethane using an evaporator. The obtained oily component was analyzed by 1H-NMR and confirmed to be dimethyldiphenoxysilane (1H-NMR (CDCl3, 500MHz, 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) 104.97 g (0.46 mol) of 2,2-bis(4-hydroxyphenyl)propane, 4.58 g (0.02 mol) of dimethyldiphenoxysilane, 101.46 g (0.47 mol) of diphenyl carbonate, and 2.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 190 °C and stirred for 20 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 20 minutes while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 1 hour and 30 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 411°C.

[0178] (Example A-2) 72.85 g (0.32 mol) of 2,2-bis(4-hydroxyphenyl)propane, 7.9 g (0.032 mol) of dimethyldiphenoxysilane, 65.86 g (0.31 mol) of diphenyl carbonate, and 0.6 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 400 Pa. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 48,035. The Tg of the above copolymer was measured using DSC and found to be 129°C. The Q value of the above copolymer was measured and found to be 75 (×10). -2 cm 3 It was / 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 amount of catalyst is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over one hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further two hours to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 400 Pa. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 54,007. The Tg of the above copolymer was measured using DSC and found to be 101°C. The Q value of the above copolymer was measured and found to be 114 (×10). -2 cm 3 It was / 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 amount of catalyst is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over one hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further two hours to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 400 Pa. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 63,068. The Tg of the above 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 amount of catalyst is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over one hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further two hours to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 400 Pa. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 49,161. The Tg of the above copolymer was measured using DSC and found to be 62°C.

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

[0183] (Example A-15) 2310 g (10.13 mol) of 2,2-bis(4-hydroxyphenyl)propane, 1849.26 g (7.58 mol) of dimethyldiphenoxysilane, 753.04 g (3.52 mol) of diphenyl carbonate, and 14.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 10 L reactor equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 180 °C and stirred for 40 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for a further 1 hour and 15 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 100 Pa. 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 that a 1% weight loss occurred at 337.1°C.

[0184] (Example A-16) 2497 g (10.95 mol) of 2,2-bis(4-hydroxyphenyl)propane, 1997.20 g (8.19 mol) of dimethyldiphenoxysilane, 813.00 g (3.80 mol) of diphenyl carbonate, and 3.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) were placed in a 10 L reactor equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 180 °C and stirred for 45 minutes. Subsequently, the transesterification reaction was carried out over 2 hours and 30 minutes while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for another 1 hour and 30 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 100 Pa. 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 that a 1% weight loss occurred at 380.6°C. Quantitative analysis of the low molecular weight compounds contained in the copolymer using GC revealed that it contained 415 ppm PhOH, 475 ppm BPA, 122 ppm DMDPS, and 44 ppm DPC.

[0185] (Reference example) Following the previously described method for measuring cyclic dimers, 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 off 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 the operation of adding ethanol dropwise to separate the precipitate from the oligomer components was repeated twice (resulting in 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 a 1000 μg / mL solution and analyzed by GC-Q-MS / FID. The result showed that the amount of cyclic dimers in the reprecipitated copolymer was 0.71 wt%. Furthermore, the Q value of the siloxane-containing polycarbonate copolymer obtained in Example A-16 was 117 (×10⁻⁶). -2 cm 3 ( / sec), the Q value of the siloxane-containing polycarbonate copolymer reprecipitate obtained in the reference example was 74 (×10 -2 cm 3 The value was ( / sec). The presence of a cyclic dimer increases the Q value, indicating high fluidity. [Table 2]

[0186] (Example A-17) 30.99 g (0.07 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 13.01 g (0.05 mol) of diphenyldimethoxysilane, 5.28 g (0.02 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate as a catalyst (catalyst amount is the number of moles relative to 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) 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 and melted at 190 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 10 minutes, while phenol and methanol distilled from the reaction system were condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 15 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 351.4°C.

[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 as a catalyst (catalyst amount is the number of moles relative to 9,9-bis(4-hydroxyphenyl)fluorene) 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 and melted at 190 °C and stirred for 15 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 20 minutes while phenol and methanol distilled from the reaction system were condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 1 hour and 30 minutes to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 361.1°C.

[0188] (Example A-19) 17.07 g (0.04 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 12.06 g (0.03 mol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 12.99 g (0.05 mol) of diphenyldimethoxysilane, 5.26 g (0.02 mol) of diphenyl carbonate, and 15.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the number of moles relative to the sum of the moles of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene) 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 and melted at 200 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 20 minutes while phenol and methanol distilled from the reaction system were condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another 1 hour and 20 minutes to obtain a browned, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 349.4°C.

[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 as a catalyst (catalyst amount is the number of moles relative to 9,9-bis(4-hydroxyphenyl)fluorene) 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 and melted at 210 °C and stirred for 25 minutes. Subsequently, over a period of 1 hour and 25 minutes, the phenol and methanol distilled from the reaction system were condensed and removed in a condenser while the transesterification reaction was carried out. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another hour to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 200 Pa. 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 that a 1% weight loss occurred at 339.1°C.

[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 as a catalyst (catalyst amount is the number of moles relative to isosorbide) 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 and melted at 100°C and stirred for 10 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 55 minutes, while methanol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 200°C and a reduced pressure of 2 hPa or less for a further 1 hour and 30 minutes to obtain a yellowed, transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 200 Pa. The Mw of 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 that a 1% weight loss occurred at 256.2°C.

[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 (catalyst amount is the relative number of moles to bis(4-hydroxyphenyl)sulfone) 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 and melted at 220 °C and stirred for 25 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 15 minutes while condensing and removing methanol distilled from the reaction system in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 1 hour and 30 minutes to obtain a transparent arylenesiloxane that had turned slightly red. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 12,806. The Tg of the above arylenesiloxane was measured using DSC and found to be 123.6°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 384.7°C.

[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 as a catalyst (catalyst amount is the relative number of moles to 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) 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 and melted at 190°C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 10 minutes while methanol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 1 hour and 30 minutes to obtain a colorless and transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 46,225. The Tg of the above arylenesiloxane was measured using DSC and found to be 97.4°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 350.6°C.

[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 as a catalyst (catalyst amount is the number of moles relative to 9,9-bis(4-hydroxyphenyl)fluorene) 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 and melted at 190 °C and stirred for 15 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes while methanol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another 1 hour and 30 minutes to obtain a yellowed, transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 27,028. The Tg of the above arylenesiloxane was measured using DSC and found to be 169.7°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 364.8°C.

[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 (catalyst amount is the relative number of moles to bis(4-hydroxyphenyl) sulfide) 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 and melted at 190°C and stirred for 15 minutes. Subsequently, the transesterification reaction was carried out over 2 hours and 15 minutes while condensing and removing methanol distilled from the reaction system in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for a further 1 hour and 20 minutes to obtain a colorless and transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 56,797. The Tg of the above arylenesiloxane was measured using DSC and found to be 73.2°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss was 391.6°C.

[0195] The results of the above-mentioned Examples A-15 to A-25 and Reference Examples are shown in Table 3. [Table 3]

[0196] (Example A-26) 37.73 g (0.07 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2-yl]fluorene, 19.47 g (0.07 mol) of dimethyldiphenoxysilane, and 30.0 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is the relative number of moles to 9,9-bis(6-hydroxynaphthyl)fluorene) 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 and melted at 210 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes, during which the phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 280°C and a reduced pressure of 2 hPa or less for a further 1 hour and 50 minutes to obtain a yellowed, transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change 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, 1,000, and 200 Pa or less. The Mw of arylenesiloxane was measured using GPC and found to be 39,353. The Tg of the above arylenesiloxane was measured using DSC and found to be 138°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 369.3°C.

[0197] (Example A-27) 61.04 g (0.33 mol) of 4,4'-dihydroxy-biphenyl, 89.64 g (0.37 mol) of dimethyldiphenoxysilane, and 3.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the number of moles relative to 4,4'-dihydroxy-biphenyl) were placed in a 200 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 220 °C and stirred for 60 minutes. Then, over the course of an hour, the phenol distilled from the reaction system is condensed and removed in a condenser. A transesterification reaction was carried out, and the system was maintained at 260°C and a reduced pressure of 1 hPa or less for 2 hours to obtain a colorless and transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 100 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 46,000. The Tg of the above arylenesiloxane was measured using DSC and found to be 70.4°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 378°C.

[0198] (Example A-28) 79.71 g (0.43 mol) of 4,4'-dihydroxy-biphenyl, 107.42 g (0.44 mol) of diphenyldimethoxysilane, and 3.0 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the number of moles relative to 4,4'-dihydroxy-biphenyl) were placed in a 200 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 220 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 2 hours while condensing and removing methanol distilled from the reaction system in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for another 2 hours to obtain a colorless and transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 17,000. The Tg of the above arylenesiloxane was measured using DSC and found to be 110°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 345°C.

[0199] (Example A-29) 39.06 g (0.21 mol) of 4,4'-dihydroxy-biphenyl, 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 as a catalyst (the amount of catalyst is the number of moles relative to 4,4'-dihydroxy-biphenyl) were placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 220 °C and stirred for 20 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for another 10 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 100 Pa. 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 that a 1% weight loss occurred at 357°C.

[0200] (Example A-30) 39.06 g (0.21 mol) of 4,4'-dihydroxy-biphenyl, 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 as a catalyst (the amount of catalyst is the number of moles relative to 4,4'-dihydroxy-biphenyl) were placed in a 300 ml four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 220 °C and stirred for 20 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes while condensing and removing methanol distilled from the reaction system in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for another 10 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 100 Pa. 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 that a 1% weight loss occurred at 363°C.

[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 amount of catalyst is the relative number of moles to 2,2'-bishydroxyethoxy-1,1'-binaphthyl) 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 and melted at 210 °C and stirred for 35 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes, during which the phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for another 1 hour and 30 minutes to obtain a colorless and transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change gradually 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 below 100 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 19,975. The Tg of the above arylenesiloxane was measured using DSC and found to be 54°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 296°C.

[0202] (Example A-32) 26.18 g (0.07 mol) of 2,2'-bishydroxyethoxy-1,1'-binaphthyl, 5.40 g (0.03 mol) of diphenyl carbonate, 12.65 g (0.05 mol) of dimethyldiphenoxysilane, and 30 μmol / mol of sodium bicarbonate as a catalyst (the amount of catalyst is the number of moles relative to 2,2'-bishydroxyethoxy-1,1'-binaphthyl) 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 and melted at 220 °C and stirred for 1 hour. Subsequently, the transesterification reaction was carried out over 1 hour and 10 minutes while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 1 hPa or less for a further 1 hour and 20 minutes to obtain a colorless, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 100 Pa. 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 that a 1% weight loss occurred at 317°C.

[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 as a catalyst (catalyst amount is the number of moles relative to isosorbide) 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 and melted at 200 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 20 minutes while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another 1 hour and 30 minutes to obtain a yellowed, transparent polycarbonate copolymer having an arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 242°C.

[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 as a catalyst (catalyst amount is the relative number of moles 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 and melted at 210 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 50 minutes, during which the phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another hour to obtain a colorless, transparent arylenesiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. The Mw of arylenesiloxane was measured using GPC and found to be 15,708. The Tg of the above arylenesiloxane was measured using DSC and found to be 51°C. The weight loss of the above arylenesiloxane was measured using TG-DTA and found that a 1% weight loss occurred at 236°C.

[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 as a catalyst (catalyst amount is the number of moles 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 and melted at 210 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 2 hPa or less for another hour to obtain a polycarbonate copolymer having a transparent arylenesiloxane structure. During the reduced pressure phase, the pressure was adjusted to change in stages 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 below 200 Pa. 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 that a 1% weight loss occurred at 252°C.

[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 amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over one hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further two hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of polyarylenesiloxane was measured using GPC and found to be 63,257. The Tg of the above copolymer was measured using DSC and found to be 54°C.

[0207] (Comparative example A-2) The Mw of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron S-3000) was measured using GPC and found to be 51,252. The Tg of the above 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 JUPIZETA EP6000, manufactured by Mitsubishi Gas Chemical Company, Inc., specifically BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) as the diol compound. The polycarbonate resin of Comparative Example A-3 had a Mw of 30000, a Q value of 97 × 10⁻² cm³ / sec, a Tg of 142°C, a refractive index (nd) of 1.638, and an Abbe number (vd) of 23.5. Compared to Comparative Example A-3, Examples A-17, 19, and 23, which used similar diol compounds, demonstrated improved fluidity (increased Q-value) without significantly altering the optical properties.

[0209] The results for Examples A-26 to A-35 and Comparative Examples A-1 and A-2 described above 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 (Mitsubishi Gas Chemical Co., Ltd., Yupiron S-3000) were kneaded and extruded at 280°C using a kneading extruder (Toyo Seiki Seisakusho Co., Ltd., Laboplastmill 4C150). The Q value of the obtained composition was 11.9 (×10⁻⁶). -2 cm 3 The result was 60.9 kJ / m². Furthermore, after drying the composition in a dryer at 110°C for 12 hours, test specimens for Charpy impact testing were molded using an injection molding machine (Shinko Celbic "C-Mobile") at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was then performed in accordance with JIS-K7111, resulting in a value of 60.9 kJ / m². 2 That was the case.

[0211] (Example A-37) 10 g of the polycarbonate copolymer obtained in Example A-4 and 190 g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron S-3000) were kneaded and extruded at 280°C using a kneading extruder (Toyo Seiki Seisakusho Co., Ltd., Laboplastmill 4C150). The Q value of the obtained composition was 14.1 (×10⁻⁶). -2 cm 3 The result was ( / sec). Furthermore, after drying the composition in a dryer at 110°C for 12 hours, test specimens for Charpy impact testing were molded using an injection molding machine (Shinko Celbic "C-Mobile") at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was then performed in accordance with JIS-K7111, and the result was 65.8 kJ / m². 2 That was the case.

[0212] (Example A-38) 150 g of the polycarbonate copolymer obtained in Example A-16 and 1850 g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron E-2000) were kneaded at a resin temperature of 280°C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH). Then, a test specimen for Charpy impact testing was formed by injection molding under conditions of a mold temperature of 80°C and a holding pressure of 90 MPa. A notched Charpy impact test was performed in accordance with JIS-K7111, and the result was 70.1 kJ / m². 2The Q value of the obtained composition was 5.5 (×10). -2 cm 3 It was / sec). (Example A-39) 300g of the polycarbonate copolymer obtained in Example A-16 and 1700g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron E-2000) were kneaded at a resin temperature of 280°C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH). Then, a test specimen for Charpy impact testing was formed by injection molding under conditions of a mold temperature of 80°C and a holding pressure of 90 MPa. A notched Charpy impact test was performed in accordance with JIS-K7111, and the result was 76.7 kJ / m². 2 The Q value of the obtained composition was 8.1 (×10). -2 cm 3 It was / sec). (Example A-40) 600g of the polycarbonate copolymer obtained in Example A-16 and 1400g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron E-2000) were kneaded at a resin temperature of 280°C using a kneading extrusion injection molding machine (high-speed injection molding machine Sodick TR100EH). Then, a test specimen for Charpy impact testing was formed by injection molding under conditions of a mold temperature of 80°C and a holding pressure of 90 MPa. A notched Charpy impact test was performed in accordance with JIS-K7111, and the result was 6.9 kJ / m². 2 The Q value of the obtained composition was 17.2 (×10). -2 cm 3 It was / sec).

[0213] (Comparative example A-4) The Q value of polycarbonate (manufactured by Mitsubishi Gas Chemical, Yupiron S-3000) is 8.0 (×10 -2 cm 3 The result was ( / sec). Furthermore, after drying the polycarbonate in a dryer at 110°C for 12 hours, a test specimen for Charpy impact testing was molded using an injection molding machine (Shinko Celbic "C-Mobile") at a resin temperature of 300°C and a mold temperature of 90°C. A notched Charpy impact test was then performed in accordance with JIS-K7111, and the result was 62.9 kJ / m². 2That was the case.

[0214] (Comparative example A-5) 2000g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Yupiron E-2000) was kneaded at a resin temperature of 300°C using a compounding 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 specimen for Charpy impact testing. A notched Charpy impact test was performed in accordance with JIS-K7111, and the result was 72.7 kJ / m². 2 The Q value of the obtained composition was 2.8 (×10). -2 cm 3 It was / sec).

[0215] The results for 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 are described below. <Weight-average molecular weight (Mw) on a polystyrene basis> Using GPC (gel permeation chromatography), a calibration curve was created using standard polystyrene with a known molecular weight (molecular weight distribution = 1) and chloroform as the developing solvent. Based on this calibration curve, the retention time of the GPC was calculated. <Glass transition temperature (Tg)> The temperature was measured using a differential thermal scanning calorimetry (DSC). The temperature was determined from the intersection point of a straight line extending the baseline from the low-temperature side to the high-temperature side of the obtained DSC curve, and a tangent line drawn at the point where the slope of the curve representing the step-like change portion of the glass transition is maximized.

[0217] (Synthesis Example 2) Synthesis of Dimethyldiphenoxysilane 7.5 g (20.2 mmol, Si molar content: 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. Next, the reaction mixture was cooled to 40°C, and then 23.7 g of a colorless oily component was obtained by vacuum distillation at 4 hPa and 150°C. The obtained oily component 1 Analysis by 1H-NMR confirmed that it was dimethyldiphenoxysilane. 1 ¹H-NMR (CDCl3, 500MHz, 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 as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of polyarylenesiloxane was measured using GPC and found to be 39,994. The Tg of 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 as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1.5 hours while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 (catalyst amount is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of polyarylenesiloxane was measured using GPC and found to be 63,257. The Tg of 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 formula (3) below, 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 after raising the temperature to 90°C, hot filtration was performed. White crystals precipitated from the resulting filtrate by leaving it at room temperature for 3 days. The crystals obtained on the filter paper were removed by filtration of the mixture after adding 10 g of heptane cooled to 5°C, and dried at 40°C under reduced pressure of 1 hPa for 45 hours, yielding 24.1 g of white powder. 1 Analysis by 1H-NMR confirmed that it is diphenyldiphenoxysilane. Diphenyldiphenoxysilane ( 1 ¹H-NMR (CDCl3, 500MHz, 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 (catalyst amount is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 260°C and a reduced pressure of 4 hPa or less for a further 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of polyarylenesiloxane was measured using GPC and found to be 24,482. The Tg of 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-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 180 °C and stirred for 30 minutes. Subsequently, an attempt was made to perform a transesterification reaction by maintaining the system temperature at 240°C and a reduced pressure of 4 hPa (400 Pa) or less, but the starting materials were removed by distillation 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 as a catalyst (the amount of catalyst is the number of moles relative to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the system was heated to 240°C over 1.5 hours under normal pressure, and then maintained at that temperature for another 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of 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 (or 16.6 mmol / mol) of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles to 2,2-bis(4-hydroxyphenyl)propane) 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 and melted at 180 °C and stirred for 30 minutes. Subsequently, the transesterification reaction was carried out over 1 hour while phenol distilled from the reaction system was condensed and removed in a condenser. The system was then maintained at 240°C and a reduced pressure of 4 hPa or less for a further 1.5 hours to obtain a colorless, transparent polyarylenesiloxane. The Mw of a 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-necked flask equipped with a stirrer. Subsequently, the system was immediately subjected to a transesterification reaction under a pressure of 240°C and a reduced pressure of 4 hPa (400 Pa) or less, but the starting materials were evaporated, and the reaction did not proceed.

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

Claims

1. In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silicon compound comprising at least one cyclic siloxane compound and a linear siloxane compound. A silane compound selected from, Carbonate compounds and, The process includes a polymerization step of polymerizing an aromatic diol compound or a diol compound containing an alicyclic diol compound, A method for producing a polycarbonate copolymer having siloxane structural units represented by any of formulas (1-1) to (1-4) and polycarbonate structural units represented by any of formulas (3-1) to (3-4), while removing alcohol derived from the carbonate compound under reduced pressure in a molten state during the polymerization process. 【Chemistry 1】 (In formulas (1-1) to (1-4), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３０ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J １ each independently represents an integer of 0 or more and 5 or less, K １ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, X is either a single bond or one of the structural formulas represented by the following formula (2): 【Chemistry 2】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Transformation 3】 (In formulas (3-1) to (3-4), R １３ ~R ２０ and R ４０ ~R ５１ Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z ３ and Z ４ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J ２ Each of these independently represents an integer between 0 and 5, K ２ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, Y is either a single bond or one of the structural formulas represented by formula (4). 【Chemistry 4】 (In the formula, R ２１ , and R ２２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ２１ and R ２２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive).

2. Z １ ~Z ４ Each of these is independently an alkylene group having 1 to 3 carbon atoms, which may have substituents. J １ and J ２ Each of these independently represents an integer between 0 and 2, K １ and K ２ Each of these independently represents an integer between 0 and 2, A method for producing a polycarbonate copolymer according to claim 1.

3. The aforementioned X is R １１ and R １２ A siloxane constituent unit representing a fluorene ring structure formed by the bonding of these units with each other, and / or, the Y is R ２１ and R ２２ A method for producing a polycarbonate copolymer according to claim 1 or 2, comprising polycarbonate constituent units representing a fluorene ring structure formed by the bonding of these units to one another.

4. In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silicon compound comprising at least one cyclic siloxane compound and a linear siloxane compound. A silane compound selected from, The process includes a polymerization step of polymerizing a carbonate compound with a diol compound containing an aromatic diol compound or an alicyclic diol compound. A method for producing a polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), while removing alcohol derived from the carbonate compound under reduced pressure in a molten state during the polymerization process. 【Transformation 5】 (In formula (1), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X is one of the structural formulas represented by the following formula (2): 【Transformation 6】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Transformation 7】 (In the formula, R １３ ~R ２０ Each independently has hydrogen, halogen, alkoxy, and substituent. A C1-C20 alkyl group may also be a C2-C20 alkenyl group which may have substituents. This represents a group, or an aryl group having 6 to 30 carbon atoms which may have substituents. Y is one of the structural formulas represented by equation (4), 【Transformation 8】 (In the formula, R ２１ , and R ２２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ２１ and R ２２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive).

5. A method for producing a polycarbonate copolymer according to any one of claims 1 to 4, wherein the transesterification catalyst comprises an alkali metal compound and / or an alkaline earth metal.

6. The method for producing a polycarbonate copolymer according to claim 5, wherein the alkali metal compound and / or alkaline earth metal compound includes a carbonate.

7. A method for producing a polycarbonate copolymer according to any one of claims 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 molar ratio. －７ ~1.0 x 10 －２ The method for producing a polycarbonate copolymer according to any one of claims 1 to 7.

9. A method for producing a polycarbonate copolymer according to any one of claims 1 to 8, wherein the reaction temperature in the polymerization step is in the range of 150°C to 300°C.

10. A method for producing a polycarbonate copolymer according to any one of claims 1 to 9, further comprising a depressurization step of gradually reducing the reaction pressure to 400 Pa or less in the polymerization step.

11. A method for producing a polycarbonate copolymer according to any one of claims 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. A method for producing a polycarbonate copolymer according to any one of claims 1 to 11, wherein no solvent is used in the polymerization step.

13. A method for producing a polycarbonate copolymer according to any one of claims 1 to 12, wherein the ratio of the total number of moles of the carbonate compound and the diaryloxysilane compound used in the polymerization step to the number of moles of the diol compound is 0.9 or more and 1.2 or less.

14. A method for producing a polycarbonate copolymer according to any one of claims 1 to 13, wherein the number of moles of the siloxane constituent units in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate constituent units is 1 to 1000.

15. A method for producing a polycarbonate copolymer according to any one of claims 1 to 14, wherein the molar ratio of the siloxane constituent unit to the polycarbonate constituent unit is 0.01:99.99 to 99.99:0.

01.

16. The Q value of the aforementioned polycarbonate copolymer, measured under the conditions of 280°C and 160 kgf, was 8 (×10⁻¹⁰). －２ cm ３ s －１ A method for producing a polycarbonate copolymer according to any one of claims 1 to 15, wherein the above is true.

17. A polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), wherein the low molecular weight compound with a weight-average molecular weight of 1,000 or less accounts for 30% by weight or less. 【Chemistry 9】 (In formulas (1-1) to (1-4), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J １ Each of these independently represents an integer between 0 and 5, K １ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, X is either a single bond or 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, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Chemistry 11】 (In formulas (3-1) to (3-4), R １３ ~R ２０ and R ４０ ~R ５１ Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z ３ and Z ４ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J ２ Each of these independently represents an integer between 0 and 5, K ２ Each of these independently represents an integer between 0 and 5, A １ and A ２ each independently represents either -O- or -CH- L １ and L ２ Each of these independently represents an integer between 0 and 3, Y is either a single bond or one of the structural formulas represented by formula (4). 【Chemistry 12】 (wherein, 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 together represent a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent, c and d each independently represent an integer between 0 and 5000 (inclusive).

18. Z １ ~Z ４ Each of these is independently an alkylene group having 1 to 3 carbon atoms, which may have substituents. J １ and J ２ Each of these independently represents an integer between 0 and 2, K １ and K ２ Each of these independently represents an integer between 0 and 2, The polycarbonate copolymer according to claim 17.

19. The aforementioned X is R １１ and R １２ A siloxane constituent unit representing a fluorene ring structure formed by the bonding of these units with each other, and / or, the Y is R ２１ and R ２２ The polycarbonate copolymer according to claim 17 or 18, having polycarbonate constituent units that represent a fluorene ring structure formed by the bonding of these units to one another.

20. A polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), wherein the proportion of low molecular weight compounds with a weight-average molecular weight of 1,000 or less, calculated from the GPC area ratio, is 30% by weight or less. 【Chemistry 13】 (In formula (1), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X is one of the structural formulas represented by the following formula (2): 【Chemistry 14】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Chemistry 15】 (In the formula, R １３ ~R ２０ Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Y is one of the structural formulas represented by equation (4), 【Chemistry 16】 (In the formula, R ２１ , and R ２２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ２１ and R ２２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive).

21. The polycarbonate copolymer according to any one of claims 17 to 20, wherein the number of moles of the siloxane constituent units in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate constituent units is 1 to 1000.

22. The polycarbonate copolymer according to any one of claims 17 to 21, wherein the molar ratio of the siloxane constituent unit to the polycarbonate constituent unit is 0.01:99.9 to 99.9:0.

01.

23. The polycarbonate copolymer according to claim 22, wherein the molar ratio of the siloxane constituent units to the polycarbonate constituent units is 30.00:70.00 to 99.9:0.

01.

24. The Q value measured under conditions of 280°C and 160 kgf was 8 (×10⁻⁶). －２ cm ３ s －１ ) The polycarbonate copolymer according to any one of claims 17 to 23.

25. A polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), wherein the total content of the cyclic body represented by formulas (5-1) to (5-3) is 4.0% by weight or less. 【Chemistry 17】 (In formulas (1-1) to (1-4), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J １ Each of these independently represents an integer between 0 and 5, K １ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, X is either a single bond or one of the structural formulas represented by the following formula (2): [Chemistry 18] (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Chemistry 19】 (In formulas (3-1) to (3-4), R １３ ~R ２０ and R ４０ ~R ５１ Each of these independently represents hydrogen, a halogen, an alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z ３ and Z ４ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J ２ Each of these independently represents an integer between 0 and 5, K ２ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, Y is either a single bond or one of the structural formulas represented by formula (4). 【Chemistry 20】 (In the formula, R ２１ , and R ２２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ２１ and R ２２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. c and d each independently represent an integer between 0 and 5000 (inclusive). 【Chemistry 21】 (In equations (5-1) to (5-3), m and n are (-OSi(R) in each ring body) １ R ２ This represents the total number of constituent units including the )O-) part and the total number of constituent units including the (-OC(=O)O-) part, respectively. (In equation (5-1), m represents an integer from 2 to 10, In equation (5-2), n represents an integer between 2 and 10. In equation (5-3), the sum of the values ​​of m is between 1 and 10, and the sum of the values ​​of n is between 1 and 10, and in equation (5-3), (-OSi(R １ R ２ The arrangement of the constituent units containing the )O-) part and the constituent units containing the (-OC(=O)O-) part is arbitrary. In formulas (5-1) to (5-3), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R １３ ~R ２０ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X １ and X ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5, X is either a single bond or one of the structural formulas represented by the following formula (2): 【Chemistry 22】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

26. A polycarbonate copolymer according to any one of claims 17 to 25, wherein the total content of the cyclic bodies of formulas (6-1) to (6-2) is 2.0% by weight or less. 【Chemistry 23】 (In equations (6-1) and (6-2), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３０ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X １ and X ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5, n represents an integer between 2 and 10. X is either a single bond or one of the structural formulas represented by the following formula (2): 【Chemistry 24】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

27. The polycarbonate copolymer according to any one of claims 17 to 26, wherein the 1% mass loss thermal decomposition temperature is 415°C or lower.

28. A composition containing a polycarbonate copolymer and a polycarbonate resin according to any one of claims 17 to 27.

29. The composition according to claim 28, wherein the total Si content in the composition is 0.1 to 20% by mass.

30. The Q value of the above composition is the Q value measured under the conditions of 280°C and 160 kgf. １ However, Q is the Q value obtained by measuring only the polycarbonate resin contained in the composition under the same conditions. ２ The composition according to any one of claims 28 and 29, wherein the amount is 120% or more.

31. A molded article obtained by molding a polycarbonate copolymer according to any one of claims 17 to 27.

32. An optical lens comprising a polycarbonate copolymer according to any one of claims 17 to 27.

33. An optical lens obtained by molding the composition described in any one of claims 28 to 30.

34. An oxysilane compound comprising at least one of a diaryloxysilane compound which is a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, and a diarykoxysilane compound which is a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane, The process includes a polymerization step of polymerizing an aromatic diol compound or a diol compound containing 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, wherein the amount of the transesterification catalyst relative to the diol compound is 0.01 μmol / mol to 16,000 μmol / mol in molar ratio. A method for producing a polysiloxane compound, comprising producing a poly(arylene / alkylene)siloxane compound having a weight-average molecular weight of 10,000 to 300,000 and containing a constituent unit represented by any of the following formulas (1-1') to (1-4'). 【Chemistry 25】 (In formulas (1-1') to (1-4'), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３０ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J １ Each of these independently represents an integer between 0 and 5, K １ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, I understand １ ~m ４ represents the total number of constituent units in each formula, and is a natural number between 10 and 1000. X is either a single bond or one of the structural formulas represented by the following formula (2): 【Chemistry 26】 (In the formula, R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

35. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 3 carbon atoms, which may have substituents. J １ Each of these independently represents an integer between 0 and 2, K １ Each of these independently represents an integer between 0 and 2, A method for producing a polysiloxane compound according to claim 34.

36. The aforementioned X is R １１ and R １２ A siloxane constituent unit representing a fluorene ring structure formed by the bonding of these units with each other, and / or, the Y is R ２１ and R ２２ A method for producing a polysiloxane compound according to claim 34 or 35, comprising polycarbonate constituent units representing a fluorene ring structure formed by the bonding of these units to one another.

37. The process includes a polymerization step of polymerizing a diaryloxysilane compound, which contains 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 the 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 molar ratio. A method for producing a polysiloxane compound, comprising a constituent unit represented by the following formula (1) and having a weight-average molecular weight of 10,000 to 300,000. 【Chemistry 27】 (In the formula, R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. m represents a natural number between 10 and 1000, X is one of the structural formulas represented by the following formula (2): 【Chemistry 28】 (In the formula, R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

38. A method for producing a polysiloxane compound according to any one of claims 34 to 37, wherein the reaction temperature in the polymerization step is in the range of 150°C to 300°C.

39. A method for producing a polysiloxane compound according to any one of claims 34 to 38, wherein the reaction pressure in the polymerization step is 101,300 Pa or less.

40. A method for producing a polysiloxane compound according to any one of claims 34 to 39, further comprising a vacuum step of gradually reducing the reaction pressure to 400 Pa or less in the polymerization step.

41. A method for producing a polysiloxane compound according to any one of claims 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 molar ratio.

42. A method for producing a polysiloxane compound according to any one of claims 34 to 41, wherein the transesterification catalyst comprises an alkali metal compound and / or an alkaline earth metal compound.

43. The method for producing a polysiloxane compound according to claim 41, wherein the alkali metal compound and / or alkaline earth metal compound comprises one or more carbonates, hydroxides, oxides, and alkoxy compounds.

44. The method for producing a polysiloxane compound according to claim 42, wherein the alkali metal compound and / or alkaline earth metal compound is a carbonate.

45. A method for producing a polysiloxane compound according to any one of claims 34 to 44, wherein no solvent is used in the polymerization step.

46. A method for producing a polysiloxane compound according to any one of claims 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. A method for producing a polysiloxane compound according to any one of claims 34 to 46, wherein in the polymerization step, the oxysilane compound or the diaryloxysilane compound is polymerized with the diol compound or the aromatic diol compound at a reaction temperature higher than 200°C and / or under reduced pressure.

48. A polysiloxane compound comprising a constituent unit represented by any 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 the cyclic product represented by formula (5-4) of 4.0% by weight or less. 【Chemistry 29】 (In formulas (1-1) to (1-4), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３０ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. J １ Each of these independently represents an integer between 0 and 5, K １ Each of these independently represents an integer between 0 and 5, A １ and A ２ Each of these independently represents either -O- or -CH-. L １ and L ２ Each of these independently represents an integer between 0 and 3, X is either a single bond or one of the structural formulas represented by the following formula (2): 【Transformation 30】 (In the formula, R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive). 【Chemistry 31】 (In equation (5-4), the arrangement of the constituent units represented by equation (5-4) and other constituent units is arbitrary, and the sum of the values ​​of m is between 2 and 10.) R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X １ and X ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5, m represents an integer between 2 and 10. X is either a single bond or one of the structural formulas represented by the following formula (2): 【Chemistry 32】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

49. The polysiloxane compound according to claim 48, wherein the total content of the cyclic products of formulas (6-1) to (6-2) is 4.0% by weight or less. 【Transformation 33】 (In equations (6-1) and (6-2), R １ , and R ２ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aryl group having 6 to 30 carbon atoms, R ３ ~R １０ and R ３０ ~R ３３ Each of these independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have substituents, an alkenyl group having 2 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents. X １ and X ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. i and ii each independently represent integers between 0 and 5, n represents an integer between 2 and 10. X is either a single bond or one of the structural formulas represented by the following formula (2): 【Transformation 34】 (In formula (2), R １１ , and R １２ Each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R １１ and R １２ This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. a and b each independently represent integers between 0 and 5000 (inclusive).

50. The polysiloxane compound according to claim 48 or 49, wherein the 1% mass loss thermal decomposition temperature is 415°C or lower.

51. A composition comprising a polysiloxane compound produced by the manufacturing method described in any one of claims 34 to 46 or a polysiloxane compound described in any one of claims 48 to 50, and a polycarbonate resin.

52. The composition according to claim 51, wherein the total Si content in the composition is 0.1 to 20% by mass.

53. The Q value of the above composition is the Q value measured under the conditions of 280°C and 160 kgf. １ However, Q is the Q value obtained by measuring only the polycarbonate resin contained in the composition under the same conditions. ２ The composition according to any one of claims 51 and 52, wherein the amount is 120% or more.

54. A molded article obtained by molding a polysiloxane compound produced by the manufacturing method described in any one of claims 34 to 46 or a polysiloxane compound described in any one of claims 48 to 50.

55. An optical lens comprising a polysiloxane compound produced by the manufacturing method described in any one of claims 34 to 46, or a polysiloxane compound described in any one of claims 48 to 50.

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