Thermoplastic resin, composition, molded article, optical lens, and method for manufacturing thermoplastic resin

Abstract

The present invention provides thermoplastic resins having siloxane structural units with excellent heat resistance and flame retardancy, particularly thermoplastic resins suitable for optical applications, and compositions containing such thermoplastic resins. [Solution] A thermoplastic resin containing a constituent unit (A) represented by general formula (I) is provided. TIFF2026090606000042.tif42132 (In general formula (I), R a ~R d Each independently represents a hydrogen atom, a halogen atom, an alkyl group with a total of 1 to 20 carbon atoms (which may have substituents), or an aryl group with a total of 6 to 30 carbon atoms (which may have substituents); each independently represents an alkyl group with a total of 1 to 20 carbon atoms (which may have substituents), or an aryl group with a total of 6 to 30 carbon atoms (which may have substituents); the substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group; and m represents an integer from 1 to 3.

Description

[Technical Field]

[0001] The present invention relates to thermoplastic resins, compositions containing thermoplastic resins, methods for producing thermoplastic resins, and the like. [Background technology]

[0002] Thermoplastic resins are formed into various molded products using simple and highly productive processing methods such as injection molding, and are used in a wide range of industrial fields, including electrical and electronic equipment, office automation equipment, heavy electrical machinery, precision machinery, and automobiles. However, conventional thermoplastic resins do not always achieve sufficiently high heat resistance or flame retardancy. Conventional thermoplastic resins may also have poor chemical resistance.

[0003] Furthermore, polymers of aromatic polysiloxanes, also known as polyarylenesiloxanes, are known as materials for molded products (for example, Patent Document 1). In recent years, the importance of polysiloxane compounds such as polyarylenesiloxanes has increased, and polyarylenesiloxanes are used, for example, as release layers in photocopying, photoresist materials, plasticizers for polycarbonates, and components of powder surface coating systems.

[0004] Polysiloxane compounds, such as polyarylenesiloxanes, tend to have relatively high heat resistance and flame retardancy, but these properties are not always sufficiently excellent. Furthermore, while methods for producing polysiloxane compounds 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 2), ensuring safety is desired.

[0005] Furthermore, thermoplastic 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]

[0006] [Patent Document 1] Special Publication No. 08-502537 [Patent Document 2] Special Publication No. 2015-512999 [Non-patent literature]

[0007] [Non-Patent Document 1] Journal of Polymer Science, Vol.18, 3119-3127(1980) [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The present invention provides thermoplastic resins having siloxane structural units with excellent heat resistance and flame retardancy, particularly thermoplastic resins suitable for optical applications, and compositions containing such thermoplastic resins.

[0009] Furthermore, the present invention provides a safe and efficient method for manufacturing thermoplastic resins containing siloxane structural units. Specifically, it provides a method for efficiently manufacturing thermoplastic resins containing siloxane structural units without generating corrosive substances such as hydrochloric acid or acetic acid, and without requiring the use of solvents, thereby reducing the environmental burden. [Means for solving the problem]

[0010] The present invention provides thermoplastic resins, compositions containing thermoplastic resins, molded articles, etc., which contain siloxane structural units and have excellent heat resistance and flame retardancy. The present invention also provides a method for producing thermoplastic resins containing siloxane structural units. The production method of the present invention does not produce environmentally harmful by-products such as acids, and can be carried out without solvents, particularly without solvents that require safety considerations.

[0011] [1] A thermoplastic resin containing a constituent unit (A) represented by the following general formula (I). [Chemical formula] (In general formula (I), R a ~R d each independently represents a hydrogen atom, a halogen atom, 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. Xa and Xb each independently represent an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent. The substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group. m represents an integer of 1 to 3. [2] Further, the thermoplastic resin according to [1] above, containing at least one of structural units (B-1) to (B-4) represented by any one of the following general formulas (II-1) to (II-4). [Chemical formula] (In general formulas (II-1) to (II-4), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent. R 3 ~R 10 , R 21 ~R 26 and R 31 ~R 36 each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent. Z1 and Z2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent. J1 each independently represents an integer of 0 to 5. K1 each independently represents an integer of 0 to 5. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. A1 and A2 each independently represent either -O- or -CH2-. L1 and L2 each independently represent integers from 0 to 3. X is either a single bond or one of the structural formulas represented by the following formulas (1) to (7): [ka] (In general formulas (1) to (7), R 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, 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. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. r and s each independently represent integers between 0 and 5000. [3] The thermoplastic resin according to [1] above, wherein the molar ratio of the constituent unit (A) to the total of the constituent units (B-1) to (B-4) is 0.1:99.9 to 100:0. [4] Furthermore, the thermoplastic resin according to any one of [1] to [3] above, comprising at least one of the constituent units (C-1) to (C-4) represented by any of the following general formulas (III-1) to (III-4). [ka] (In general formulas (III-1) to (III-4), R 3 ~R 10 , R 21 ~R 26 and R 31 ~R 36Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted C1-C5 alkoxy group, an optionally substituted C1-C20 alkyl group, an optionally substituted C2-C20 alkenyl group, or an optionally substituted C6-C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. Each J1 independently represents an integer from 0 to 5. Each K1 independently represents an integer from 0 to 5. A1 and A2 each independently represent either -O- or -CH2-. L1 and L2 each independently represent integers from 0 to 3. X is either a single bond or one of the structural formulas represented by the following formulas (1) to (7): [ka] (In general formulas (1) to (7), R 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, 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. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. r and s each independently represent integers between 0 and 5000. [5] The thermoplastic resin according to [4] above, wherein the molar ratio of the total of constituent units (A) and (B-1) to (B-4) to the total of constituent units (C-1) to (C-4) is 0.1:99.9 to 100:0. [6] The thermoplastic resin described in [1] above, comprising only the constituent unit (A). [7] In the above general formula (I), R a ~R d A thermoplastic resin according to any one of the above [1] to [6], wherein Xa is hydrogen and Xb are methyl groups. [8] A thermoplastic resin according to any of [1] to [7] above, wherein the weight-average molecular weight (Mw) on a polystyrene basis is 10,000 to 300,000. [9] A thermoplastic resin according to any of [1] to [8] above, wherein the low molecular weight compound with a weight-average molecular weight of 1,000 or less is 1% by weight or less.

[10] The thermoplastic resin described in [9] above, wherein the proportion calculated from the GPC area ratio of low molecular weight compounds with a weight-average molecular weight of 1,000 or less is 1% by weight or less.

[11] A thermoplastic resin according to any of [1] to

[10] above, wherein the 1% mass loss thermal decomposition temperature is 300°C or higher.

[12] A thermoplastic resin according to any of [1] to

[11] above, wherein the weight loss rate at 500°C is 40% or less.

[0012]

[13] A composition containing a thermoplastic resin and a polycarbonate resin as described in any of [1] to

[12] above. [13-1] The composition according to

[13] , wherein the Q value Q1 of the composition measured under the conditions of 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.

[0013]

[14] A molded article comprising a thermoplastic resin as described in any of [1] to

[12] above.

[15] An optical lens comprising a thermoplastic resin as described in any of [1] to

[12] above.

[16] An optical lens obtained by molding the composition described in

[13] above.

[0014]

[17] A diaryloxysilane compound which is any of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, and an oxysilane compound which is any of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane, At a minimum, a diol compound represented by the following general formula (IV) and It has a polymerization step for polymerizing the [ka] (In general formula (IV), R a ~R d Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group with a total of 1 to 20 carbon atoms which may have substituents, or an aryl group with a total of 6 to 30 carbon atoms which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. m represents an integer between 1 and 3. In the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure using a catalyst while removing the resulting aryl alcohol and / or alkyl alcohol. A method for producing a thermoplastic resin, comprising a constituent unit (A) represented by the following general formula (I). [ka] (In general formula (I), R a ~R d Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group with a total of 1 to 20 carbon atoms which may have substituents, or an aryl group with a total of 6 to 30 carbon atoms which may have substituents. Xa and Xb each independently represent 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, which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. m represents an integer between 1 and 3.

[18] A method for producing a thermoplastic resin according to

[17] , wherein in the polymerization step, a catalyst containing an alkali metal compound and / or an alkaline earth metal compound is used.

[19] A method for producing a thermoplastic resin according to

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

[20] A method for producing a thermoplastic resin according to

[17] above, wherein a catalyst containing a phosphorus compound is used in the polymerization step.

[21] A method for producing a thermoplastic resin according to

[20] , wherein the phosphorus compound comprises a compound represented by the following general formula (8). (PRe4) + (Xc) - ...(8) (In general formula (8), each Re independently represents an alkyl group, an aryl group, or an alkylaryl group, and multiple Re groups may be bonded to each other to form a ring structure.) Xc represents a hydroxyl group, halogen atom, alkyloxy group, aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, HCO3, or BRf4 (where Rf is independently a hydrogen atom, alkyl group, or aryl group).

[22] A method for producing a thermoplastic resin according to any one of

[17] to

[21] above, wherein the weight-average molecular weight of the thermoplastic resin is 10,000 to 300,000.

[23] The amount of the catalyst used in the polymerization step relative to the diol compound is 1.0 × 10 in molar ratio. -7 ~1.0×10 -2 A method for producing a thermoplastic resin as described in any of the above

[17] to

[22] .

[24] A method for producing a thermoplastic resin according to any one of

[17] to

[23] above, wherein the reaction temperature in the polymerization step is in the range of 150°C to 300°C.

[25] A method for producing a thermoplastic resin according to any one of

[17] to

[24] above, further comprising a vacuum step in which the reaction pressure is gradually reduced from 24,000 Pa or more to less than 100 Pa in the polymerization step.

[26] A method for producing a thermoplastic resin according to any one of

[17] to

[25] above, wherein in the polymerization step, the oxysilane compound and the diol compound are polymerized under a pressure of less than 100 Pa.

[27] A method for producing a thermoplastic resin according to any one of

[17] to

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

[28] A method for producing a thermoplastic resin according to any one of

[17] to

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

[29] A molecular weight measurement step for measuring the molecular weight of the thermoplastic resin produced in the polymerization step, A method for producing a thermoplastic resin according to any one of

[17] to

[28] , further comprising an additional polymerization step of repolymerizing the thermoplastic resin whose molecular weight is lower than a predetermined target value. [Effects of the Invention]

[0015] According to the present invention, it is possible to realize thermoplastic resins having siloxane structural units with excellent heat resistance and flame retardancy, particularly thermoplastic resins suitable for optical applications, as well as compositions and molded articles containing such thermoplastic resins. Furthermore, according to the present invention, thermoplastic resins having siloxane structural units can be manufactured by a safe and efficient manufacturing method. [Brief explanation of the drawing]

[0016] [Figure 1] This graph shows the DSC chart of the resin (SiHQ) obtained in Example 1-1. [Figure 2] This graph shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 1-1 and 3-5 and Comparative Examples 1 and 2. [Figure 3]This graph shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 1-1, 1-2, and 6-8 and Comparative Example 2. [Figure 4] This graph shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 2 and 9 and Comparative Examples 1 and 2. [Figure 5] This is a side view showing the shape of the three-point bending load jig used to evaluate chemical resistance in each example and comparative example. [Modes for carrying out the invention]

[0017] First, the thermoplastic resin of the present invention will be described in detail.

[0018] <1. Thermoplastic resin> [(I) Siloxane constituent unit: Constituent unit (A)] The thermoplastic resin of the present invention is a polymer having siloxane structural units, and specifically includes at least structural unit (A) represented by the following formula (I). [ka] In general formula (I), R a ~R d Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group with a total of 1 to 20 carbon atoms that may have substituents, or an aryl group with a total of 6 to 30 carbon atoms that may have substituents. The total number of carbon atoms in the alkyl group that may have substituents is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The total number of carbon atoms in the aryl group that may have substituents is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. R a ~R d Preferably, this is a hydrogen atom, 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 which may have substituents, and more preferably, a hydrogen atom.

[0019] In general formula (I), Xa and Xb each independently represent 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, which may have substituents. The total number of carbon atoms of the alkyl and aryl groups is determined by R a ~R d It is similar to that. Xa and Xb are preferably a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms, which may have substituents; more preferably a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms; and particularly preferably a methyl group.

[0020] In general formula (I), the substituents described above are any of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group, the total number of carbon atoms of the alkenyl group and alkynyl group is preferably 2 to 10, more preferably 2 to 5, and the total number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 5.

[0021] In general formula (I), m is an integer between 1 and 3, preferably 1 or 2. That is, the constituent unit (A) is preferably a constituent unit derived from hydroquinone or its derivative (m=1), or a constituent unit derived from 4,4'-biphenyldiol or its derivative (m=2).

[0022] In thermoplastic resins, it is preferable to include structural units in which -(O[Ph(Ra~d)]m- moieties and -(OSi(Xa)(Xb)-) moieties are alternately repeated, as shown in formula (I). Thus, it is preferable for thermoplastic resins to be random copolymers rather than block copolymers that contain portions in which only -(O[Ph(Ra~d)]m- moieties are repeated in large numbers and portions in which only -(OSi(Xa)(Xb)-) moieties are repeated in large numbers. For example, the thermoplastic resin preferably has structural units in the following general formula (Ia) where the value of n, which indicates the number of alternating repetitions between the -(O[Ph(Ra~d)]m- moiety and the -(OSi(Xa)(Xb)-) moiety, is 10 or more, more preferably 20 or more, even more preferably 30 or more, even more preferably 50 or more, and particularly preferably 100 or more. [ka] Thus, thermoplastic resins with many regions in which -(O[Ph(Ra~d)]m- moieties and -(OSi(Xa)(Xb)-) moieties are alternately linked, and which are obtained by random copolymerization, tend to have easier char formation at high temperatures and superior heat resistance and flame retardancy compared to block copolymers.

[0023] [(II) Additional siloxane constituent units: Constituent units (B)] The thermoplastic resin may consist only of the above-described constituent unit (A), but it may also have other constituent units. For example, an additional constituent unit of a thermoplastic resin may be at least one of the constituent units (B-1) to (B-4) represented by general formulas (II-1) to (II-4), respectively. [ka]

[0024] In general formulas (II-1) to (II-4), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms that may have substituents, or an aryl group having 6 to 30 carbon atoms that may have substituents. The total number of carbon atoms in the alkyl group that may have substituents is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 5. The total number of carbon atoms in the aryl group that may have substituents is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12.

[0025] In general formulas (II-1) and (II-2), R 3 ~R 10 , R 21 ~R 26 and R 31 ~R 36 Each of these is independently a hydrogen atom, a halogen atom, an optionally substituted C1-C5 alkoxy group, an optionally substituted C1-C20 alkyl group, an optionally substituted C2-C20 alkenyl group, or an optionally substituted C6-C30 aryl group. R 3 ~R 10 , R 21 ~R 26 and R 31 ~R 36 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 , R 21 ~R 26 and R 31 ~R 36 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 , R 21 ~R 26 and R 31 ~R 36 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.

[0026] In general formulas (II-1) to (II-3), Z1 and Z2 are each independently C1 to C5 alkylene groups which may have substituents. Z1 and Z2 are preferably C1 to C3 alkylene groups, and more preferably C1 or C2 alkylene groups. In general formulas (II-1) to (II-3), J1 is an integer between 0 and 5, and K1 is an integer between 0 and 5, independently of each other. J1 and K1 each represent an integer between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2. In general formulas (II-1) to (II-3), A1 and A2 are each independently either -O- or -CH2-. Also, L1 and L2 are each independently integers from 0 to 3. L1 and L2 are preferably 1 or 2.

[0027] In general formulas (II-1) to (II-4), the substituents are any of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. The total number of carbon atoms in the alkenyl group and alkynyl group is preferably 2 to 10, more preferably 2 to 5, and the total number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 5.

[0028] In general formulas (II-1) to (II-2), X is either a single bond or one of the structural formulas represented by the following formulas (1) to (7). [ka]

[0029] In general formulas (1) to (7), R 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, an alkyl group with a total of 1 to 20 carbon atoms which may have substituents, or an aryl group with a total of 6 to 30 carbon atoms which may have substituents, or R 11 and R 12The carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, is formed by the bonding of these atoms to each other. The total number of carbon atoms of the alkyl group, which may have substituents, is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 5. The total number of carbon atoms of the aryl group, which may have substituents, is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. Furthermore, in general formulas (1) to (7), the substituents mentioned above are one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. r and s are each independent integers between 0 and 5000, preferably between 0 and 1000, and more preferably between 0 and 500.

[0030] The constituent units (B-1) to (B-4), represented by general formulas (II-1) to (II-4), respectively, can be added to the constituent unit (A) in any proportion. However, the ratio of the number of moles of constituent unit (A) (a) to the total mole ratio of constituent units (B-1) to (B-4) (b) is preferably a:b = 0.1:99.9 to 100:0. The molar ratio of a:b is preferably 10:90 to 95:5, more preferably 20:80 to 90:10, even more preferably 30:70 to 80:20, and particularly preferably 30:70 to 70:30.

[0031] [(III) Polycarbonate constituent units: Constituent unit (C)] The thermoplastic resin may consist of at least one of the above-described constituent units (A) and (B-1) to (B-4), for example, only constituent units (A) and (B-1), but it may also have other constituent units. For example, an additional constituent unit of a thermoplastic resin may be at least one of the constituent units (C-1) to (C-4) represented by general formulas (III-1) to (III-4), respectively. [ka]

[0032] In general formulas (III-1) and (III-2), R 3 ~R 10 、R 21 ~R 26 and R 31 ~R 36 are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent. R 3 ~R 10 、R 21 ~R 26 and R 31 ~R 36 When R ~R 3 ~R 10 、R 21 ~R 26 and R 31 ~R 36 are an alkyl group which may have a substituent, it is preferable that the total number of carbon atoms is 1 to 10, more preferably the total number of carbon atoms is 1 to 4, and particularly preferably the total number of carbon atoms is 1 or 2. Also, when R 3 ~R 10 、R 21 ~R 26 and R 31 ~R 36 are an alkenyl group which may have a substituent, it is preferable that the total number of carbon atoms is 2 to 10, more preferably the total number of carbon atoms is 2 to 6, and particularly preferably the total number of carbon atoms is 2 to 4.

[0033] In general formulas (III-1) to (III-4), the substituents are any of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. The total number of carbon atoms in the alkenyl group and alkynyl group is preferably 2 to 10, more preferably 2 to 5, and the total number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 5.

[0034] In general formulas (III-1) to (III-3), Z1 and Z2 are each independently C1 to C5 alkylene groups which may have substituents. Z1 and Z2 are preferably C1 to C3 alkylene groups, and more preferably C1 or C2 alkylene groups.

[0035] In general formulas (II-1) to (II-3), J1 is an integer between 0 and 5, and K1 is an integer between 0 and 5, independently of each other. J1 and K1 each represent an integer between 0 and 5, preferably between 0 and 3, and more preferably between 0 and 2, such as 1 or 2.

[0036] In general formulas (II-1) to (II-3), A1 and A2 are each independently either -O- or -CH2-. Also, L1 and L2 are each independently integers from 0 to 3. L1 and L2 are preferably 1 or 2.

[0037] In general formulas (III-1) to (III-2), X is either a single bond or one of the structural formulas represented by the following formulas (1) to (7). [ka] Equations (1) to (7) above are equivalent to equations (1) to (7) in general equations (II-1) to (II-2).

[0038] Constituent units (C-1) to (C-4), represented by general formulas (III-1) to (III-4), can be added to constituent unit (A), or to constituent units (A) and (B), in any proportion. However, the ratio of the total number of moles of constituent units (A) and (B) (a+b) to the total mole ratio c of constituent units (C-1) to (C-4) is preferably (a+b):c = 0.1:99.9 to 100:0. The mole ratio of (a+b):c is preferably 10:90 to 95:5, more preferably 20:80 to 90:10, even more preferably 30:70 to 80:20, and particularly preferably 30:70 to 70:30.

[0039] Other resins The thermoplastic resin of the present invention may contain resins other than the thermoplastic resin of the present invention, as necessary, as long as the desired physical properties are not significantly impaired. Other resins such as those described above include, for example, thermoplastic polyester resins other than the thermoplastic resin of the present invention, such as polycarbonate resin, 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); elastomers such as core / shell type elastomers and polyester elastomers, such as methyl methacrylate-acrylic rubber-styrene copolymer (MAS); polyolefin resins such as cyclic cycloolefin resin (COP resin) and cyclic cycloolefin (COP) copolymer resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); and polycaprolactone.

[0040] [(IV) Properties of thermoplastic resins] Next, we will explain the properties of thermoplastic resins. The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 10,000 to 200,000, even more preferably 15,000 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. Thus, the lower limit of the weight-average molecular weight of the thermoplastic resin is preferably 10,000, more preferably 15,000, and even more preferably 20,000.

[0041] When thermoplastic resins are not used alone but as a composition mixed with other resins, it is sometimes desirable to significantly increase the proportion of the siloxane structural unit (A) mentioned above. For example, thermoplastic resins with a high Si content and a proportion of siloxane structural unit (A) 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. Furthermore, when applications that increase the proportion of siloxane structural units are preferred, the upper limit of the proportion of siloxane structural unit (A) mentioned above is not limited to 90%, but may be, for example, 92%, 95%, 98%, etc.

[0042] In thermoplastic resins, the glass transition temperature (Tg) in accordance with JIS K 7121 is preferably -30 to 130°C, more preferably -20 to 120°C, and more preferably -10 to 100°C.

[0043] In thermoplastic resins, it is preferable that the amount of low molecular weight compounds with a weight-average molecular weight of 1,000 or less is 1% by weight or less, more preferably 0.5% by weight or less, and even more preferably 0.2% by weight or less. Thermoplastic resins 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) relatively quickly when injection molding or other processes are continuously performed to manufacture discs or complex and thin-walled products. In this regard, if the amount of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in the thermoplastic resin is 1% by mass or less, mold contamination can be effectively prevented. Furthermore, although the lower limit of the content of low molecular weight compounds with a weight-average molecular weight of 1,000 or less in thermoplastic resins is not particularly important, it may be, for example, 0.001% by weight, 0.01% by weight, or 0.1% by weight.

[0044] The content of the low molecular weight compounds mentioned above in thermoplastic resins 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. In other words, the proportion of low molecular weight compounds with a molecular weight (weight-average molecular weight) of 1,000 or less in thermoplastic resins 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.

[0045] In thermoplastic resins, the total content of cyclic bodies 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 thermoplastic resin. If the content of these cyclic dimers is within the above-mentioned range, the properties of the thermoplastic resin, 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, respectively, in each annular structure. That is, in the annular structure of equation (5-1), if constituent units other than those containing the (-OSi(R1R2)O-) moiety are included, and in the annular structure 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 shown in the equation in the annular structure, respectively. In particular, equation (5-3) includes annular structures 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 shown in the equation in the annular structure, 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 formula (5-3), the value of m, i.e., the total number of constituent units containing the (-OSi(R1R2)O-) moiety in the annular body, is 1 to 10, and the value of n, i.e., the total number of constituent units containing the (-OC(=O)O-) moiety in the annular body, is 1 to 10. Furthermore, m and n are preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. As mentioned above, in the ring body of equation (5-3), the arrangement of the constituent units containing the (-OSi(R1R2)O-) moiety and the constituent units containing the (-OC(=O)O-) moiety 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. In formulas (5-1) to (5-3), i and ii each independently represent an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably 1 or 2. Also, in formulas (5-1) to (5-3), R 1 , R 2 , R 3 ~R 10 , R 13 ~R 20 and X are the same as R 1 , R 2 , R 3 ~R 10 , R 13 ~R 20 and X in formulas (1-1) and (1-2), respectively.

[0046] Also, as specific examples of each of the compounds of formulas (5-1) to (5-3), the cyclic bodies of the following formulas (5-1’) to (5-3’) can be mentioned.

Chemical formula

[0047] In the thermoplastic resin, the 1% mass loss thermal decomposition temperature is preferably 300°C or higher, more preferably 320°C or higher, still more preferably 330°C or higher, and particularly preferably 350°C or higher.

[0048] In the thermoplastic resin, the mass loss ratio at 500°C measured by the method described later is preferably 40% or less, more preferably 30% or less, still more preferably 25% or less, even more preferably 20% or less, and particularly preferably 17% or less. In other words, the mass retention rate (%) at 500°C for thermoplastic resins, which is the value of 100 - "mass loss rate at 500°C (%)", is preferably 60% or more, more preferably 70% or more, even more preferably 75% or more, even more preferably 80% or more, and particularly preferably 83% or more.

[0049] In thermoplastic resins, the ratio of the total weight of silicon atoms (total Si amount) based on the total weight of the thermoplastic resin is preferably 0.1 to 20% by mass or 0.1 to 17% 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).

[0050] Next, a composition according to the present invention, that is, a composition containing the thermoplastic resin described above, will be described in detail.

[0051] <2. Composition> The composition of the present invention includes the thermoplastic resin described above, that is, the thermoplastic resin described in section <1. Thermoplastic Resin> above, and a polycarbonate resin that does not fall under the category of the thermoplastic resin described above. Examples of polycarbonate resins that do not fall under the category of the thermoplastic resin described above include polycarbonate resins that do not contain siloxane structures (constituent unit (A)) completely or substantially.

[0052] The types of polycarbonate resins that do not fall under the thermoplastic resins described above 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 thermoplastic resins described above may also include polyester carbonate. Similarly, 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.

[0053] The weight-average molecular weight of polycarbonate resins that do not fall under the thermoplastic resins described above is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.

[0054] 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.

[0055] 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 thermoplastic resin, 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 thermoplastic resin, 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.

[0056] Compositions with excellent properties can be manufactured using thermoplastic resins with a high Si content. By mixing a thermoplastic resin 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, and its heat resistance and flame retardancy can also be further improved.

[0057] Furthermore, in compositions containing thermoplastic resins, 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, may be included. Since phenolic compounds and diphenyl carbonate (DPC), which are impurities, can cause a decrease in strength and odor generation when molded, 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.

[0058] Next, a molded article according to the present invention, which includes a thermoplastic resin, will be described. <3. Molded body> The molded article according to the present invention is obtained by molding the above-mentioned thermoplastic resin, or a composition containing a thermoplastic resin, 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.

[0059] Furthermore, the optical lens according to the present invention is obtained by molding the thermoplastic resin of the present invention, or a composition containing the thermoplastic resin, etc. The thermoplastic resin of the present invention is suitable for optical applications, and the optical lens of the present invention has a refractive index, Abbe number, etc., within a range suitable for use as a lens.

[0060] Molded bodies other than lenses There are no restrictions on the shape, pattern, color, dimensions, etc., of molded articles obtained using thermoplastic resins; 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, and covers and cases for lighting fixtures. 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, and portable radios and audio players. 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 thermoplastic resin of the present invention has excellent impact resistance and high fluidity when melted, and can be formed into molded articles with a fine structure, making it suitable for use as electrical and electronic components, mechanical parts, and vehicle parts for use in automobiles. Examples of such parts include automotive interior panels, automotive lamp lenses, automotive inner lenses, automotive lens protective covers, and automotive light guides.

[0061] Manufacturing method for molded products 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 insulated molds, molding using rapidly heated molds, foam molding (including supercritical fluids), 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 to manufacture the molded article.

[0062] <4. Method for manufacturing thermoplastic resins> The method for producing the thermoplastic resin of the present invention having the above-described structure and properties comprises a polymerization step of polymerizing an oxysilane compound and an aromatic diol compound in the presence of a catalyst.

[0063] The reaction in the polymerization process is schematically shown below. For example, when a diol compound such as hydroquinone (HQ) or 4,4'-biphenyldiol (BP) is reacted with a diaryloxysilane compound (Si(CH3)2(OPh)2), which is an example of a silane compound having two methyl groups and a phenoxy group, a thermoplastic resin is obtained as shown in formula (A) or (B) below. [ka] In these polymerization reactions, by-products may include alcohols derived from silane compounds, such as aryl alcohols like phenol (PhOH) shown in formulas (A) and (B). Therefore, in the polymerization step, the polymerization reaction is carried out under reduced pressure while the mixture of the above components is molten, removing by-products such as aryl alcohols like phenol and alkyl alcohols.

[0064] Details regarding the manufacturing method of thermoplastic resins, including raw materials such as oxysilane compounds and diol compounds, are as follows. The oxysilane compounds used in the production of thermoplastic resins can be selected from diaryloxysilane compounds and diarykoxysilane compounds. Diaryloxysilane compounds include dialkyldiaryloxysilanes, diaryldiaryloxysilanes, and monoalkylmonoaryldiaryloxysilanes. Furthermore, dialkoxysilane compounds include dialkyldialkoxysilanes, diaryldialkoxysilanes, and monoalkylmonoaryldialkoxysilanes. These oxysilane compounds are specifically as follows:

[0065] [I. Oxysilane compounds] The oxysilane compound used in the polymerization process is used to form siloxane structural units (structural unit (A)) in thermoplastic resins, as shown in formula (A) above. The oxysilane compound is not particularly limited as long as it can be formed in the main chain of the thermoplastic resin, but it is selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound).

[0066] In the polymerization process, for example, a silane compound containing at least one diaryloxysilane compound (details to be described later), at least one dialkoxysilane compound, and at least one silicon compound is used. 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, or 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. The diaryloxysilane compounds will be described below.

[0067] (I-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.

[0068] 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 b 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 a and R bHowever, 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.

[0069] 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.

[0070] As is clear from formula (A) above, the aryloxy group (OAr group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but rather produces 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.

[0071] Specific examples of dialkyldiaryloxysilanes include dimethyldiphenoxysilane, methylethyldiphenoxysilane, and diethyldiphenoxysilane, while specific examples of diaryldiaryloxysilanes include diphenyldiphenoxysilane. Furthermore, specific examples of monoalkylmonaryldiaryloxysilanes include methylphenylphenoxysilane.

[0072] [II. 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.

[0073] 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.

[0074] Specific examples of dialkyldialkoxysilanes include dimethyldimethoxysilane, methylethyldimethoxysilane, and diethyldimethoxysilane, while specific examples of diaryldialkoxysilanes include diphenyldimethoxysilane. Furthermore, specific examples of monoalkylmonoaryldialkoxysilanes include methylphenyldimethoxysilane.

[0075] [III. 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.

[0076] (III-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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] (III-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 e and 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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, and mercapto groups.

[0086] 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.

[0087] 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.

[0088] [IV. Diol Compounds] Diol compounds represented by the following general formula (IV) are used in the polymerization process of thermoplastic resins. [ka] In general formula (IV), R a ~R d and m are, respectively, R in general formula (I). a ~R d It is synonymous with m.

[0089] Aromatic diol compounds are used to constitute the main chain of polycarbonate copolymers, as shown in the above formulas (A) and (B) which outline the polymerization reaction. In addition to the above-mentioned hydroquinone (HQ) and 4,4'-biphenyldiol (BP), aromatic diol compounds used in the polymerization process include the following: For example, 2-methyl-1,4-benzenediol, 2,3-dimethyl-1,4-benzenediol, 2,6-dimethyl-1,4-benzenediol, 2,3,5-trimethyl-1,4-benzenediol, 2,3,5,6-tetramethyl-1,4-benzenediol, [1,1'-biphenyl]-4,4'-diol, 3-methyl-[1,1'-biphenyl]-4,4'-diol, 3,3'-dimethyl-[1,1'-biphenyl]-4,4'-diol, 3,5-dimethyl-[1,1'-biphenyl]-4,4'-diol, 3,3'',5,5''-tetramethyl-[1,1'-biphenyl] Examples include -4,4'-diol, 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diol, [1,1':4',1''-terphenyl]-4,4''-diol, 3-methyl-[1,1':4',1''-terphenyl]-4,4''-diol, 3,5-dimethyl-[1,1':4',1''-terphenyl]-4,4''-diol, 3,3''-dimethyl-[1,1':4',1''-terphenyl]-4,4''-diol, and 3,3'',5,5''-tetramethyl-[1,1':4',1''-terphenyl]-4,4''-diol. Among these, hydroquinone (HQ) and 4,4'-biphenyldiol (BP) are preferred as aromatic diol compounds.

[0090] In the polymerization process, in addition to the aromatic diols described above, alicyclic diol compounds and the like may also be used. In the polymerization process, it is preferable that the aromatic diol represented by formula (IV) described above is used in an amount of 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more of the aromatic diol represented by formula (IV) is used as the diol compound.

[0091] In the polymerization process, the above-mentioned oxysilane compound and the above-mentioned diol compound are polymerized under reduced pressure in a molten state using a catalyst while removing the resulting aryl alcohol and / or alkyl alcohol. In this way, a thermoplastic resin containing, for example, the constituent unit (A) represented by the above-mentioned general formula (I) is obtained.

[0092] [V. Catalyst] The following catalysts are used in the polymerization process.

[0093] (V-1) Alkali metal catalyst As catalysts used in the polymerization process, catalysts containing basic compounds are preferred. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Such compounds include organic acid salts, inorganic salts such as carbonates, oxides, hydroxides, hydrides, or alkoxides of alkali metal compounds and alkaline earth metal compounds. 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 catalyst is more preferably an alkali metal carbonate or alkali metal hydroxide among the basic compound catalysts mentioned above. Specific examples of more preferred catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. The catalysts mentioned above can be prepared by known methods, or commercially available catalysts may be used.

[0094] (V-2) Phosphorus-based catalyst Catalysts containing phosphorus compounds are also suitably used in the polymerization process. The phosphorus-based catalyst preferably contains at least a compound represented by the following general formula (8). (PRe4) + (Xc) - ...(8) In general formula (8), each Re independently represents an alkyl group, an aryl group, or an alkylaryl group, and multiple Re groups may bond to each other to form a ring structure, preferably an aryl group having 6 to 16 carbon atoms. In general formula (8), Xc is a hydroxyl group, a halogen atom, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO3, or BRf4 (where Rf is independently a hydrogen atom, an alkyl group, or an aryl group), preferably an aryloxy group containing an aryl group having 6 to 16 carbon atoms, and BRf4 containing an aryl group having 6 to 16 carbon atoms as Rf4. These aryl groups having 6 to 16 carbon atoms are preferably aryl groups having 6 to 12 carbon atoms, and more preferably aryl groups having 6 to 8 carbon atoms.

[0095] Specific examples of phosphorus-based catalysts include biphenyltriphenylphosphonium hydroxide, biphenyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium phenoxide, biphenyltriphenylphosphonium chloride, tetraphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphonium phenoxide, naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, and naphthylphenyltriphenylphosphonium chloride. Of these, tetraphenylphosphonium phenoxide and tetraphenylphosphonium tetraphenylborate are particularly preferred.

[0096] [VI. Reaction conditions for the polymerization process] In the polymerization process, the mixture of the above-mentioned components is melted, and under reduced pressure in the molten state, the by-products, aryl alcohol or alkyl alcohol, are removed. By setting the reaction conditions in this way, the polymerization reaction can proceed efficiently.

[0097] In the polymerization process, it is preferable to gradually reduce the reaction pressure and then adjust it to a predetermined level. That is, in the polymerization process, it is preferable to maintain a state of atmospheric pressure or a state with little or no pressure reduction for a certain period of time without reducing the pressure, and then reduce the pressure in the system to further advance the polymerization reaction. Specifically, it is preferable to set the pressure to a value of 24,000 Pa or higher, then gradually reduce it to less than 100 Pa, and then proceed with the polymerization reaction under the reduced pressure. For example, in the polymerization process, it is preferable to gradually reduce the reaction pressure from the initial atmospheric pressure to less than 100 Pa, 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 less than 100 Pa. This vacuum process, in which the reaction system is reduced in stages and the degree of vacuum is increased midway through, is preferable because it allows for efficient removal of by-products such as alcohol while suppressing the distillation of the raw materials. Furthermore, regardless of whether there is a gradual decrease or not, it is preferable to adjust the reaction pressure to less than 100 Pa.

[0098] 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.

[0099] 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.

[0100] Furthermore, the silane compounds and aromatic diol compounds described 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.

[0101] In the polymerization process, the ratio of the molar amount of catalyst to the molar amount of aromatic diol compound (molar ratio: i.e., the value of molar amount of 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).

[0102] In the polymerization process, the molar ratio of aromatic diol compounds (diol compounds) to silane compounds (oxysilane compounds) (i.e., the value of the number of moles of silane compounds / the number of moles of aromatic diol compounds) is, for example, 0.8 to 1.3, preferably 0.9 to 1.2 or 0.9 to 1.25, and more preferably 0.95 to 1.2. Furthermore, in the polymerization process, the molar ratio of aromatic diol compounds (diol compounds) to the total number of moles of diaryl carbonate and silane compounds (oxysilane compounds) (i.e., the value of (total number of moles of diaryl carbonate and silane compounds) / number of moles of aromatic diol compounds) is preferably 0.9 or more and 1.2 or less, and more preferably 0.95 or more and 1.15 or less.

[0103] [VII. Molecular weight measurement process and additional polymerization process] In the method for producing thermoplastic resins, a molecular weight measurement step may be performed to measure the molecular weight of the thermoplastic resin obtained in the polymerization step, for example, the weight-average molecular weight. The method for measuring molecular weight is described below. Furthermore, a predetermined target value may be set for the molecular weight of the thermoplastic resin produced by the polymerization process, for example, the weight-average molecular weight (Mw). If the measured molecular weight falls outside the range of the target value, especially if it is lower than the target value, an additional polymerization step may be performed to polymerize the thermoplastic resin again.

[0104] Specific examples of target molecular weights for thermoplastic resins include the preferred ranges of weight-average molecular weight (Mw) mentioned above, such as 10,000 to 300,000, 10,000 to 200,000, 15,000 to 100,000, 20,000 to 80,000, 30,000 to 70,000, and 40,000 to 65,000. Furthermore, from the viewpoint of preventing insufficient polymerization, only the lower limit of the weight-average molecular weight may be set as the target value. For example, target lower limits could be 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, and 35,000 or more.

[0105] The duration of the additional polymerization step is determined appropriately, taking into account various conditions, similar to the polymerization step. For example, the duration of the additional polymerization step can range from 20 minutes to 5 hours, 30 minutes to 4 hours, 1 to 3 hours, or 1.5 to 2.5 hours. Furthermore, the polymerization reaction temperature in the additional polymerization step 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, for example, 220 to 260°C.

[0106] (Regarding secondary components) Inactivator In the thermoplastic resin of the present invention, the catalyst may be removed or deactivated after the polymerization reaction for production is completed in order to maintain thermal stability and hydrolysis stability. For example, a method of deactivating the catalyst by adding a known 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.

[0107] additives <Stabilizer> Stabilizers may be added to the thermoplastic resin and molded article 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 thermoplastic resin. The stabilizer may contain only one type or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0108] <<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. When a heat 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 0.03 parts by mass or more, per 100 parts by mass of thermoplastic resin, 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. 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.

[0109] <<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 blended, 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 thermoplastic resin. 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.

[0110] The thermoplastic resin and molded articles of the present invention may contain various additives in addition to the secondary components described above, without departing from the spirit of the present invention. Examples of additives include at least one additive selected from flame retardants, flame retardant aids, 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.

[0111] <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 thermoplastic resin. 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.

[0112] <Flame retardant> The thermoplastic resin and molded articles of the present invention may contain, as flame retardants, organometallic salt-based flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, and the like. 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. Specific examples of flame retardants (flame retardant compositions) include halogen-based flame retardants, organometallic salt-based flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, antimony-based flame retardants, or flame retardant additives.

[0113] <Release agent> Examples of release agents that may be included in thermoplastic resins and molded articles 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. The proportion of the release agent to be added 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, and more preferably 1 part by mass or less, per 100 parts by mass of thermoplastic resin. 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.

[0114] <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 blended, 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 thermoplastic resin. 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. [Examples]

[0115] <Weight-average molecular weight (weight-average molecular weight (Mw) on a polystyrene basis)> 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(Wi × Mi) / Σ(Wi) (In the above formula, i represents the i-th division point when the molecular weight M is divided, Wi represents the i-th weight, and Mi represents the i-th molecular weight. 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

[0116] <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) Furthermore, using the method described above, it was also possible to measure the melting point (Tm) along with Tg.

[0117] <Thermal decomposition temperature> 1% - Temperature at which thermal mass loss begins and the percentage of mass loss at 500°C A 10 mg sample was accurately weighed into an aluminum pan (Al open-type sample container, φ5.2 H2.5 mm). The measurement was performed under atmospheric pressure. 0.00519 g of α-alumina was used as the reference material. The sample temperature was adjusted to 30°C and heated to 500°C at a rate of 10°C / min. The temperature at which 1% mass loss occurred was defined as "1% - onset temperature of thermal mass loss". The percentage of mass loss of the sample at 500°C, relative to the mass of the sample before heating, was defined as "500°C mass loss percentage (%)". The table below shows the "mass retention rate at 500°C (%)", i.e., 100 - "500°C mass loss percentage (%)". Measuring device: Simultaneous differential thermal and thermal mass measuring device (TG / DTA) (manufactured by Hitachi High-Tech Science, TG / DTA7300)

[0118] <Thermal analysis (melting point, etc.)> As a measurement sample, a 5 mg test piece was 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 -10°C at a rate of 20°C / min. After that, the sample was heated back up 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)

[0119] <Forming of test specimens> The resin and resin composition pellets obtained in the examples described later were dried at 120°C for 4 hours in a hot air circulating dryer. Subsequently, ISO multipurpose test specimens (3 mm and 4 mm thick) were molded using an injection molding machine under the conditions of cylinder temperature 280°C, mold temperature 80°C, and molding cycle of 45 seconds. A Sodick "PE100" (product name) injection molding machine was used. More specifically, we manufactured Type A test specimens according to ISO 3167:93 (JIS K 7139:96) and used them for the following evaluation tests.

[0120] <Charpy impact test> Using the aforementioned ISO multipurpose test specimen with a thickness of 3 mm, a Charpy impact test (with notch, unit: kJ / m2) was performed at 23°C in accordance with the ISO-179 standard.

[0121] <Liquidity (Q-value)> This represents the melting flow volume per unit time (ml / sec) measured at 280℃ and a load of 160kg (the melting flow volume was measured using a Shimadzu Corporation CFT-500D type (nozzle diameter 1mm x nozzle length 10mm), and the value per unit time was calculated from a stroke of 7.0~10.0mm).

[0122] <Evaluation of Flame Retardancy (LOI)> The aforementioned ISO multipurpose test specimen, 4 mm thick, was placed in a constant temperature chamber at 23°C and 50% relative humidity for 88 hours and tested using a Candle Combustion Test Machine AC2 (manufactured by Toyo Seiki Seisakusho) in accordance with JIS-K-7201-2. In this test, specimens with a Combustion Oxygen Index (LOI value) of 26 or higher are considered to have flame retardant properties (self-extinguishing properties). In the table below, the evaluation item for flame retardancy will be abbreviated as "LOI".

[0123] <Chemical Resistance Test> In an environment of 23°C, a jig (three-point bending load jig 1) capable of applying a three-point bending load, as shown in Figure 5 below, was used. The 4mm thick ISO multipurpose test specimen obtained above was mounted in the lower center of the specimen mounting jig 2 shown in Figure 5, and then the chemicals listed in Table 1 below were applied to it. A crimping adjustment cylinder 3 for adjusting the amount of strain was attached to the specimen mounting jig 2, and the specimen was fixed with a wing nut 4, allowing the amount of strain to be adjusted to 0.72% or 0.24%. A 4mm thick ISO multipurpose test specimen was fixed to the test specimen mounting fixture 2 and crimped to achieve a strain of 0.72% or 0.4%. After 8 to 24 hours, the molded product was released from the crimp, the applied chemicals were wiped off, and the chemical resistance was visually checked according to the following criteria. Excellent condition: No noticeable cosmetic defects. Good; the above-mentioned cosmetic defects are present, but they are minor or the defect rate is less than 50%. Defect: The above-mentioned cosmetic defects are present, making it difficult to use. [Table 1]

[0124] (Example 1-1) <Colbenzcalcium / Catalyst: Tetraphenylphosphonium phenoxide> 38.54 g (0.35 mol) of hydroquinone (HQ), 85.42 g (0.35 mol) of dimethyldiphenoxysilane, and 10 μmol / mol of tetraphenylphosphonium phenoxide as a catalyst (the amount of the catalyst is the relative number of moles to hydroquinone) were placed in a 300 ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 190 °C and stirred for 10 minutes. Then, the phenol flowing out from the reaction system was condensed with a condenser and removed over 110 minutes while the reaction was carried out. The inside of the reaction system was brought to 220 °C and less than 1 hPa, and further held for 90 minutes to obtain a colorless polysiloxane. During depressurization, the pressure was adjusted to change stepwise to less than 43,000 Pa, 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, 100 Pa. When the GPC measurement of the obtained polysiloxane was carried out, Mw was 43,046. When the DSC measurement of this polysiloxane was carried out, the glass transition temperature (Tg) was -0.6 °C. As a result of measuring the weight loss using TG-DTA, the 1% weight loss temperature was 331 °C. Other properties of the polysiloxane obtained in Example 1-1 were as follows. Molar ratio of raw materials HQ:BPA (bisphenol A) = 10:0 Mw 43,046 Mn 13,734 Mw / Mn 3.134 Tg -0.6 °C 1% weight loss temperature (°C) 331 °C 3% weight loss temperature (°C) 372 °C 5% weight loss temperature (°C) 393 °C 10% weight loss temperature (°C) 430 °C Weight retention rate (%) at 500 °C 87% 500 °C weight loss rate (%) 13% Furthermore, the DSC chart of the thermoplastic resin (SiHQ) obtained in Example 1-1 is shown in Figure 1.

[0125] (Examples 1-2) <Colbenscale / Catalyst: Cesium Carbonate> 38.54 g (0.350 mol) of hydroquinone, 86.02 g (0.353 mol) of dimethyldiphenoxysilane, and 3 μmol / mol of cesium carbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) 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 30 minutes. Subsequently, the transesterification reaction was carried out over 130 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 250 °C and less than 1 hPa, and maintained for another 90 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 27,000 Pa, 20,000 Pa, 16,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 64,261. The Tg (transition time) of the polysiloxane was 0°C, and the Tm (melting point) was 103°C. These Tg and Tm values ​​were generally consistent across the examples abbreviated as SiHQ (Examples 1-1 to 1-3, 1-5, and 1-6). In other words, in these examples, the Tg of the polysiloxane was approximately 0°C, within the range of -1°C to 1°C.

[0126] (Examples 1-3) <Bench scale: Repolymerization of a resin that has undergone one polymerization> 1.349 kg (12.25 mol) of hydroquinone, 3.035 kg (12.44 mol) of dimethyldiphenoxysilane, and 3 μmol / mol of cesium carbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) were placed in a 10 L reaction vessel equipped with a helical ribbon 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 120 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser, bringing the system temperature to less than 250 °C and 1 hPa, and maintaining this pressure for another 120 minutes. After that, the system was returned to atmospheric pressure with nitrogen to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the polysiloxane obtained at this stage revealed a Mw of 26,798. Next, the obtained polysiloxane was pulverized and placed back into the same reaction vessel, where it was dried under reduced pressure. Then, the polysiloxane was melted at 190 °C, stirring was started, and the temperature was raised to 250 °C. After holding it at this temperature for 140 minutes, it was restored to pressure with nitrogen to obtain a colorless polysiloxane. GPC measurement of this polysiloxane revealed a Mw of 39,700.

[0127] (Examples 1-4) PC resin (manufactured by Mitsubishi Gas Chemical Company, Yupiron® E2000) and SiHQ resin obtained from Examples 1-3 (the above Mw=39,700 SiHQ obtained by two polymerizations) were weighed to the amounts (by weight %) shown in Table 2 below. After mixing in a tumbler for 15 minutes, the mixture was melt-kneaded at a cylinder temperature of 280°C using a vented twin-screw extruder (Toyo Seiki Mfg. Co., Ltd. "Twin-screw segment extruder 2D30WS"), and a pelletized resin composition was obtained by strand cutting.

[0128] (Examples 1-5) <Bench scale, prolonged heating / Catalyst: Cesium carbonate> 2.292 kg (20.81 mol) of hydroquinone, 5.151 kg (21.11 mol) of dimethyldiphenoxysilane, and 3 μmol / mol of cesium carbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) were placed in a 10 L reaction vessel equipped with a helical ribbon 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 150 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser, bringing the system temperature to less than 250 °C and 1 hPa, and maintaining this for another 240 minutes. After that, the system was returned to atmospheric pressure with nitrogen to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 43,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 39,970.

[0129] (Examples 1-6) <Colubenscal, prolonged heating / Catalyst: sodium bicarbonate> 77.08 g (0.700 mol) of hydroquinone, 173.34 g (0.710 mol) of dimethyldiphenoxysilane, and 12 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount relative to hydroquinone) were placed in a 500 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 100 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 240 °C and less than 1 hPa, and maintained for another 180 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 27,000 Pa, 24,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 6,000 Pa, 2,000 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 66,267.

[0130] (Comparative examples A~D) ·Comparative example A Only PC resin (manufactured by Mitsubishi Engineering Plastics, aromatic PC: Yupiron S3000) was used. ·Comparative example B Only commercially available siloxane polymers having the following structure were used (Si-PC EXL1414T). [ka] ·Comparative example C In Comparative Example C ("SiBPA-PC"), a polymer mainly composed of the same components as in Examples 1-4 (aromatic PC: Eupylone E2000) was produced as follows, following the steps of Examples 1-4. 2,2-bis(4-hydroxyphenyl)propane 2370.77 g (10.40 mol), dimethyldiphenoxysilane 1859.19 g (7.62 mol), diphenyl carbonate 750.97 g (3.51 mol), and tetraphenylphosphonium phenoxide 10.0 μmol / mol as a catalyst (catalyst amount 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 190°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 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, 4,000 Pa, 2,000 Pa, and below 100 Pa. The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC and found to be 34,647. PC resin (manufactured by Mitsubishi Engineering Plastics, aromatic PC: Yupiron E2000N) and the SiBPA-PC resin obtained from the above were weighed in the amounts shown in Table 2 below. After mixing in a tumbler for 15 minutes, the mixture was melt-kneaded at a cylinder temperature of 280°C using a vented twin-screw extruder (Toyo Seiki Mfg. Co., Ltd. "Twin-screw segment extruder 2D30WS"), and a pelletized resin composition was obtained by strand cutting. ·Comparative example D A pelletized resin composition was obtained in the same manner as in Comparative Example C, except that the amounts of PC resin (manufactured by Mitsubishi Engineering Plastics, aromatic PC: Yupiron E2000) and the SiBPA-PC resin obtained above were as shown in Table 2 below. The results of evaluating Examples 1-4 described above and their comparative examples A-D are shown in Table 2 below.

Table 2

[0131] As described above, according to each embodiment, it was confirmed that thermoplastic resins excellent in various properties such as impact resistance, fluidity, flame retardancy, and chemical resistance can be obtained. Also, in order to mainly adjust the molecular weight of the thermoplastic resin to be produced, it was useful to repolymerize the resin obtained by one polymerization (Examples 1-3) and to extend the time of the polymerization reaction (Examples 1-5). In particular, although there was a tendency that the molecular weight of the thermoplastic resin to be produced was less likely to increase when the scale was larger than that in Examples 1-1, 1-2, and 1-6 performed on the Corvus scale, in Examples 1-3 and 1-5 performed on the bench scale, thermoplastic resins with a sufficiently high molecular weight were produced by repolymerization or extension of the reaction time.

[0132] (Example 2) As raw materials, 61.4 g (0.33 mol) of 4,4'-biphenyldiol (BP), 90.28 g (0.37 mol) of dimethyldiphenoxysilane (DMDPS), and 3 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles with respect to 4,4'-biphenyldiol) were used, and the reaction was carried out in the same manner as in Example 1-1. The physical properties of the obtained resin are shown in Table 3.

[0133] (Comparative Example 1) As raw materials, 18.24 g (0.08 mol) of bisphenol A (BPA), 21.96 g (0.09 mol) of dimethyldiphenoxysilane (DMDPS), and 7 μmol / mol of cesium carbonate as a catalyst (the amount of catalyst is the relative number of moles with respect to bisphenol A) were used, and the reaction was carried out in the same manner as in Example 1-1. The physical properties of the obtained resin are shown in Table 3.

[0134]

Table 3

[0135] (Example 3) The reaction was carried out in the same manner as in Example 1-1, except that the raw materials used were 4.62 g (0.042 mol) of HQ, 22.3 g (0.098 mol) of bisphenol A (BPA), i.e., a molar ratio of HQ:BPA = 3:7, 35.12 g (0.14 mol) of DMDPS, and 12 μmol / mol of sodium bicarbonate as a catalyst (the amount of catalyst is the relative number of moles to the total amount of HQ and BPA). The reaction equation is shown below, and the physical properties of the obtained resin (SiHQBPA) are shown in Tables 4 and 5. [ka]

[0136] (Example 4) The reaction was carried out in the same manner as in Example 3, except that the molar ratio of HQ to BPA was changed to HQ:BPA=5:5. The physical properties of the obtained resin (SiHQBPA) are shown in Tables 4 and 5.

[0137] (Example 5) The reaction was carried out in the same manner as in Example 3, except that the molar ratio of HQ to BPA was changed to HQ:BPA=7:3. The physical properties of the obtained resin (SiHQBPA) are shown in Tables 4 and 5.

[0138] [Table 4]

[0139] [Table 5]

[0140] Figure 2 shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 1-1 and 3-5, Comparative Example 1, and Comparative Example 2 (PC) described later. Table 5 and Figure 2 show that in Comparative Example 1, the rate of thermal decomposition increased above 400°C, whereas in Examples 1-1, 3-5, SiHQBPA showed good heat resistance above 400°C at all charging ratios, and it was confirmed that it could retain about 80% of its weight even at 500°C. Furthermore, it was found that even with a mixing ratio (HQ:BPA) of 3:7, weight loss at temperatures above 400°C was mitigated. This result suggests that the addition of a small amount of HQ promotes char formation even when the BPA skeleton is largely present.

[0141] (Example 6) The reaction was carried out in the same manner as in Example 1-1, except that the raw materials used were 4.62 g (0.042 mol) of HQ, 18.21 g (0.098 mol) of BP, i.e., a molar ratio of HQ:BP = 3:7, 35.12 g (0.14 mol) of DMDPS, and 12 μmol / mol of sodium bicarbonate as a catalyst (the amount of catalyst is the number of moles relative to the total amount of HQ and BP). The reaction equation is shown below, and the physical properties of the obtained resin (SiHQBP) are shown in Tables 6 and 7. [ka]

[0142] (Example 7) The reaction was carried out in the same manner as in Example 6, except that the molar ratio of HQ to BP was changed to HQ:BP = 5:5. The physical properties of the obtained resin (SiHQBPA) are shown in Tables 6 and 7.

[0143] (Example 8) The reaction was carried out in the same manner as in Example 6, except that the molar ratio of HQ to BP was changed to HQ:BP = 7:3. The physical properties of the obtained resin (SiHQBPA) are shown in Tables 6 and 7.

[0144] (Comparative Example 2) Table 7 shows the physical properties of Yupiron S-3000N, a bisphenol A type polycarbonate resin manufactured by Mitsubishi Engineering Plastics Corporation (BPA-PC). The glass transition temperature (Tg) of the polycarbonate resin in Comparative Example 2 was 147°C. [Table 6] [Table 7]

[0145] Figure 3 shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 1-1, 1-2, and 6-8 and Comparative Example 2. Table 7 and Figure 3 show that SiBP homopolymer retains more than 95% of its weight even at 500 °C and shows almost no thermal decomposition. Furthermore, when copolymerized with HQ, it exhibits very high heat resistance in the high-temperature range, and it was confirmed that SiHQBP can retain more than 90% of its weight even at 500 °C. Comparative Example 2, which uses commercially available bisphenol A polycarbonate, showed a sharp decrease in weight retention at 500°C, and it was confirmed that no char formation occurred. In Comparative Example 2, as shown in Figure 3, the weight retention was relatively good up to approximately 450°C, but it decreased sharply at higher temperatures. On the other hand, each of the examples is superior to Comparative Example 2 in that such a sharp decrease in weight retention is not observed, making them more practical.

[0146] (Example 9) The reaction was carried out in the same manner as in Example 1-1, except that the raw materials used were BP 13.01 g (0.070 mol), BPA 15.93 g (0.070 mol), i.e., the molar ratio of HQ to BPA was HQ:BPA=5:5, DMDPS 35.12 g (0.14 mol), and sodium bicarbonate 12 μmol / mol as a catalyst (the amount of catalyst is the relative number of moles to the total amount of HQ and BPA). The reaction equation is shown below, and the physical properties of the obtained resin (SiBPBPA) are shown in Tables 8 and 9. [ka] [Table 8] [Table 9]

[0147] Figure 4 shows the relationship between the weight loss temperature and weight percentage of the thermoplastic resins obtained in Examples 2 and 9 and Comparative Examples 1 and 2. Table 9 and Figure 4 show that the heat resistance at high temperatures of Example 2 (SiBP) and Example 9 (SiBPBPA) was significantly improved compared to Comparative Example 1 (SiBPA) and Comparative Example 2 (PC), and it was confirmed that they could retain 90% of their weight even at 500°C.

[0148] (Example 10) DMDPS+HQ+D PC 15.48 g (0.14 mol) of hydroquinone, 24.02 g (0.098 mol) of dimethyldiphenoxysilane, 9.93 g (0.046 mol) of diphenyl carbonate, and 12 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) 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 130 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 220 °C and less than 1 hPa, and maintained for another 90 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 41508. DSC measurement of the above polysiloxane revealed a Tg of 24.8 °C. Weight loss was measured using TG-DTA, and the 1% weight loss temperature was found to be 307 °C. The physical properties of the obtained resins are shown in Tables 10 and 11.

[0149] (Example 11) DMDPS+BP+D PC 26.18 g (0.14 mol) of 4,4-dihydroxybiphenyl, 24.02 g (0.098 mol) of dimethyldiphenoxysilane, 9.93 g (0.046 mol) of diphenyl carbonate, and 12 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) 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 30 minutes. Subsequently, the transesterification reaction was carried out over 130 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 260 °C and less than 1 hPa, and maintained for another 90 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 70,000 Pa, 53,000 Pa, 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 38951. DSC measurement of the above polysiloxane revealed a Tg of 92.4 °C. Weight loss was measured using TG-DTA, and the 1% weight loss temperature was found to be 333 °C. The physical properties of the obtained resins are shown in Tables 10 and 11.

[0150] (Example 12) DMDPS+HQ+D PC+BPA 10.77 g (0.098 mol) of hydroquinone, 9.56 g (0.042 mol) of bisphenol-A, 23.70 g (0.097 mol) of dimethyldiphenoxysilane, 9.93 g (0.046 mol) of diphenyl carbonate, and 12 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) 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 130 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 220 °C and less than 1 hPa, and maintained for another 90 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 71001. DSC measurement of the above polysiloxane revealed a Tg of 40.3 °C. Weight loss was measured using TG-DTA, and the 1% weight loss temperature was found to be 352 °C. The physical properties of the obtained resins are shown in Tables 10 and 11.

[0151] (Example 13) DMDPS+BP+DPC+BPA 18.21 g (0.098 mol) of 4,4-dihydroxybiphenyl, 9.56 g (0.042 mol) of bisphenol-A, 23.70 g (0.097 mol) of dimethyldiphenoxysilane, 9.93 g (0.046 mol) of diphenyl carbonate, and 12 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is the number of moles relative to hydroquinone) 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 30 minutes. Subsequently, the transesterification reaction was carried out over 130 minutes while phenol leaching out of the reaction system was condensed and removed in a condenser. The system was then cooled to 220 °C and less than 1 hPa, and maintained for another 90 minutes to obtain a colorless polysiloxane. During the reduced pressure phase, the pressure was adjusted to change in stages from 70,000 Pa, 53,000 Pa, 24,000 Pa, 22,000 Pa, 20,000 Pa, 18,000 Pa, 16,000 Pa, 14,000 Pa, 12,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, 500 Pa, and less than 100 Pa. GPC measurement of the obtained polysiloxane revealed a Mw of 40839. DSC measurement of the above polysiloxane revealed a Tg of 87.5 °C. Weight loss was measured using TG-DTA, and the 1% weight loss temperature was found to be 378 °C. The physical properties of the obtained resins are shown in Tables 10 and 11.

[0152] [Table 10] [Table 11]

[0153] As described above, in the examples using hydroquinone-based compounds as diol compounds, polysiloxane resins with high heat resistance were obtained. Furthermore, SiHQ and SiBP showed suppressed weight loss, especially in the high-temperature range, and were found to form char when thermal decomposition occurred. Such SiHQ and SiBP were found to have higher heat resistance and flame retardancy compared to general Bisphenol A polycarbonate resins.

Claims

1. A thermoplastic resin containing a constituent unit (A) represented by the following general formula (I). 【Chemistry 1】 (In general formula (I), R ａ ~R ｄ Each of these independently represents a hydrogen atom, a halogen atom, 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 which may have substituents. Xa and Xb each independently represent 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, which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. m represents an integer between 1 and 3.

2. Furthermore, the thermoplastic resin according to claim 1, comprising at least one of the constituent units (B-1) to (B-4) represented by any of the following general formulas (II-1) to (II-4). 【Chemistry 2】 (In general formulas (II-1) to (II-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 ３ to R １０ , R ２１ to R ２６ and R ３１ to R ３６ each independently represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, 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 from 0 to 5. K １ Each of these independently represents an integer from 0 to 5. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. A １ and A ２ These are, independently, -O- and -CH. ２ - represents one of the following: 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 formulas (1) to (7). 【Transformation 3】 (In general formulas (1) to (7), R １１ and R １２ Each independently represents a hydrogen atom, a halogen atom, 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. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. r and s each independently represent integers between 0 and 5000.

3. The thermoplastic resin according to claim 1, wherein the molar ratio of the constituent unit (A) to the total of the constituent units (B-1) to (B-4) is 0.1:99.9 to 100:

0.

4. Furthermore, the thermoplastic resin according to any one of claims 1 to 3, comprising at least one of the constituent units (C-1) to (C-4) represented by any of the following general formulas (III-1) to (III-4). 【Chemistry 4】 (In general formulas (III-1) to (III-4), R ３ ~R １０ , R ２１ ~R ２６ and R ３１ ~R ３６ Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted C1-C5 alkoxy group, an optionally substituted C1-C20 alkyl group, an optionally substituted C2-C20 alkenyl group, or an optionally substituted C6-C30 aryl group. Z １ and Z ２ Each of these is independently an alkylene group having 1 to 5 carbon atoms, which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. J １ Each of these independently represents an integer from 0 to 5. K １ Each of these independently represents an integer from 0 to 5. A １ and A ２ These are, independently, -O- and -CH. ２ - represents one of the following: 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 formulas (1) to (7). 【Transformation 5】 (In general formulas (1) to (7), R １１ and R １２ Each independently represents a hydrogen atom, a halogen atom, 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. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. r and s each independently represent integers between 0 and 5000.

5. The thermoplastic resin according to claim 4, wherein the molar ratio of the sum of the constituent units (A) and (B-1) to (B-4) to the sum of the constituent units (C-1) to (C-4) is 0.1:99.9 to 100:

0.

6. The thermoplastic resin according to claim 1, comprising only the aforementioned structural unit (A).

7. In the above general formula (I), R ａ ~R ｄ The thermoplastic resin according to any one of claims 1 to 6, wherein is hydrogen, and Xa and Xb are methyl groups.

8. A thermoplastic resin according to any one of claims 1 to 7, wherein the weight-average molecular weight (Mw) on a polystyrene basis is 10,000 to 300,000.

9. A thermoplastic resin according to any one of claims 1 to 8, wherein the low molecular weight compound with a weight-average molecular weight of 1,000 or less is 1% by weight or less.

10. The thermoplastic resin according to claim 9, wherein the proportion calculated from the GPC area ratio of low molecular weight compounds with a weight-average molecular weight of 1,000 or less is 1% by weight or less.

11. The thermoplastic resin according to any one of claims 1 to 10, wherein the thermal decomposition temperature for a 1% mass loss is 300°C or higher.

12. A thermoplastic resin according to any one of claims 1 to 11, wherein the weight loss rate at 500°C is 40% or less.

13. A composition containing a thermoplastic resin and a polycarbonate resin according to any one of claims 1 to 12.

14. A molded article comprising the thermoplastic resin according to any one of claims 1 to 12.

15. An optical lens comprising the thermoplastic resin described in any one of claims 1 to 12.

16. An optical lens obtained by molding the composition described in claim 13.

17. 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, At a minimum, a diol compound represented by the following general formula (IV) and It has a polymerization step for polymerizing the 【Transformation 6】 (In general formula (IV), R ａ ~R ｄ Each of these independently represents a hydrogen atom, a halogen atom, 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 which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. m represents an integer between 1 and 3. In the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure using a catalyst while removing the resulting aryl alcohol and / or alkyl alcohol. A method for producing a thermoplastic resin, comprising a constituent unit (A) represented by the following general formula (I). 【Transformation 7】 (In general formula (I), R ａ ~R ｄ Each of these independently represents a hydrogen atom, a halogen atom, 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 which may have substituents. Xa and Xb each independently represent 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, which may have substituents. The substituent is one of a halogen, a cyano group, an alkenyl group, an alkynyl group, or an alkoxy group. m represents an integer between 1 and 3.

18. A method for producing a thermoplastic resin according to claim 17, wherein a catalyst containing an alkali metal compound and / or an alkaline earth metal compound is used in the polymerization step.

19. The method for producing a thermoplastic resin according to claim 18, wherein the alkali metal compound and / or alkaline earth metal compound includes a carbonate.

20. A method for producing a thermoplastic resin according to claim 17, wherein a catalyst containing a phosphorus compound is used in the polymerization step.

21. The method for producing a thermoplastic resin according to claim 20, wherein the phosphorus compound includes a compound represented by the following general formula (8). (PRe ４ ) ＋ (Xc) － ・・・(8) (In general formula (8), each Re independently represents an alkyl group, an aryl group, or an alkylaryl group, and multiple Re may be bonded to each other to form a ring structure.) Xc is a hydroxyl group, halogen atom, alkyloxy group, aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, HCO ３ , or BRF ４ (Each Rf independently represents a hydrogen atom, an alkyl group, or an aryl group.)

22. A method for producing a thermoplastic resin according to any one of claims 17 to 21, wherein the weight-average molecular weight of the thermoplastic resin is 10,000 to 300,000.

23. The amount of the catalyst used in the polymerization step relative to the diol compound is 1.0 × 10 in molar ratio. －７ ~1.0 x 10 －２ A method for producing a thermoplastic resin according to any one of claims 17 to 22.

24. A method for producing a thermoplastic resin according to any one of claims 17 to 23, wherein the reaction temperature in the polymerization step is in the range of 150°C to 300°C.

25. A method for producing a thermoplastic resin according to any one of claims 17 to 24, further comprising a vacuum step in which the reaction pressure is gradually reduced from 24,000 Pa or more to less than 100 Pa in the polymerization step.

26. A method for producing a thermoplastic resin according to any one of claims 17 to 25, wherein in the polymerization step, the oxysilane compound and the diol compound are polymerized under a pressure of less than 100 Pa.

27. A method for producing a thermoplastic resin according to any one of claims 17 to 26, wherein no solvent is used in the polymerization step.

28. A method for producing a thermoplastic resin according to any one of claims 17 to 27, wherein the ratio of the number of moles of the oxysilane compound to the number of moles of the diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

29. A molecular weight measurement step for measuring the molecular weight of the thermoplastic resin produced in the polymerization step, A method for producing a thermoplastic resin according to any one of claims 17 to 28, further comprising an additional polymerization step of repolymerizing the thermoplastic resin whose molecular weight is lower than a predetermined target value.

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