Thermoplastic resin and molded article containing thermoplastic resin

Abstract

Provided are: a thermoplastic resin having excellent properties such as refractive index and chromatic aberration in optical applications; a molded article containing such a thermoplastic resin; and the like. A thermoplastic resin having a structural unit represented by general formula (1), that is, having: a silane structural unit (S) that is a-OSi (R1R2) O-moiety; and a diol structural unit (A) derived from a dihydroxy compound represented by M. (In general formula (1), at least one of R1 and R2 represents a C10-30 polycyclic aryl group which may have a substituent. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin, particularly a thermoplastic resin containing a structural unit derived from a silane compound, and a molded article containing the thermoplastic resin. Background Art

[0002] Various thermoplastic resins have been widely used in various fields. Thermoplastic resins are formed into various molded products by methods such as injection molding, and are widely used in industrial fields such as electrical and electronic equipment, OA equipment (office automation equipment), heavy electrical equipment, precision machinery, and automobile fields.

[0003] As thermoplastic resins used as materials for molded products, there are known polymers of aromatic polysiloxanes, also known as so-called polyarylene siloxanes (e.g., Patent Document 1, Patent Document 2). In recent years, the importance of polysiloxane compounds such as polyarylene siloxanes has gradually increased, and polyarylene siloxanes are used, for example, as release layers in photocopies, photoresist materials, plasticizers for resins such as polycarbonate resins, and components of powder surface coating systems.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Publication No. 08-502537

[0007] Patent Document 2: Japanese Patent Application No. 2015-512999 Summary of the invention

[0008] Problems to be solved by the invention

[0009] It is not necessarily said that existing thermoplastic resins such as polysiloxane polymers have properties suitable for specific applications, and thermoplastic resins having excellent properties are required as materials for molded products for optical applications, etc. For example, among thermoplastic resins used for optical applications, it is generally confirmed that thermoplastic resins with high refractive index tend to have low Abbe numbers, and therefore, it is not easy to improve at least both the refractive index and the Abbe number.

[0010] As described above, from the viewpoint of properties in optical applications, for example, refractive index, chromatic aberration represented by Abbe number, etc., new thermoplastic resins having excellent properties are desired.

[0011] Technical solutions to solve problems

[0012] The present invention provides the following thermoplastic resin, a molded article containing the thermoplastic resin, and the like.

[0013] [1] A thermoplastic resin having a structural unit represented by the following general formula (1), that is, the structural unit has:

[0014] AS-OSi(R 1 R 2 )O-site silane structural unit (S), and

[0015] M represents a diol structural unit (A) derived from a dihydroxy compound.

[0016]

[0017] (In general formula (1), R 1 and R 2 At least one of represents a polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent.

[0018] [2] The thermoplastic resin according to [1], wherein R 1 and R 2 Based on the total molar number of the polycyclic aromatic groups, the ratio of the polycyclic aromatic groups is 30 mol% or more.

[0019] [3] The thermoplastic resin according to [1] or [2], wherein, based on the total number of moles of all the silane structural units (S) contained in the thermoplastic resin, in the general formula (1), R 1 and R 2 The ratio of the silane structural units which are all the polycyclic aromatic groups is 30 mol% or more.

[0020] [4] The thermoplastic resin according to any one of [1] to [3] above, wherein in the general formula (1), R 1 and R 2 are each independently selected from the group consisting of naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylenyl, naphthacenyl, and naphthacene. Chrysenyl is a polycyclic aromatic group.

[0021] [5] The thermoplastic resin according to any one of [1] to [4] above, wherein R 1 and R 2 Each is independently 1-naphthyl, 2-naphthyl or 9-phenanthrenyl.

[0022] [6] The thermoplastic resin according to any one of [1] to [5] above, wherein R 1 and R 2 One of them is a phenyl group which may have a substituent.

[0023] [7] The thermoplastic resin according to any one of [1] to [6] above, wherein the diol structural unit (A) comprises a structural unit represented by any one of the following general formula (A-1) or general formula (A-2).

[0024]

[0025] (In formulas (A-1) and (A-2), R 3 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent,

[0026] Z 1 and Z 2 are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

[0027] J 1 Each independently represents an integer from 0 to 5,

[0028] K 1 Each independently represents an integer from 0 to 5,

[0029] X is independently a single bond, or any one of the structural formulas shown in the following formula (2),

[0030]

[0031] (In formula (2), R 11 and R 12 each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, and R 11 and R 12 are combined with each other to form a carbon ring or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent,

[0032] a and b each independently represent an integer of 0 or more than 1 and less than 5000.)

[0033] [8] The thermoplastic resin according to any one of [1] to [7] above, wherein the diol structural unit (A) comprises any one of the following structural units:

[0034] A fluorene structural unit (F) as a structural unit derived from a fluorene ring-containing dihydroxy compound;

[0035] A binaphthyl structural unit (N) which is a structural unit derived from a binaphthyl-containing dihydroxy compound; and

[0036] The bisphenol structural unit (B) is derived from a bisphenol compound.

[0037] [9] The thermoplastic resin according to [8] above, wherein the fluorene structural unit (F) is a structural unit derived from any one of BPEF, BPPEF and BNEF.

[0038]

[10] The thermoplastic resin according to [8] or [9] above, wherein the binaphthalene structural unit (N) contains at least a structural unit derived from 2NBN or DPBN.

[0039]

[11] The thermoplastic resin according to [8] above, wherein the molar ratio of the fluorene structural unit (F) to the binaphthyl structural unit (N) is 30:70 to 90:10.

[0040]

[12] The thermoplastic resin described in [1] above, wherein the relationship between the refractive index (nd) and the Abbe number (νd) of the thermoplastic resin satisfies the relationship of the following formula (I).

[0041] Refractive index (nd) > -0.0078 × Abbe number (νd) + 1.8293… (I)

[0042]

[13] The thermoplastic resin according to

[12] above, wherein the formula (I) satisfies the following formula (I-1).

[0043] -0.0080×Abbe number (νd)+1.861>Refractive index (nd)>-0.0078×Abbe number (νd)+1.8293…(I-1)

[0044]

[14] The thermoplastic resin according to any one of [1] to

[13] above, wherein the refractive index (nd) of the thermoplastic resin is 1.600 to 1.730.

[0045]

[15] The thermoplastic resin according to any one of [1] to

[14] above, wherein the Abbe number (νd) of the thermoplastic resin is 15.0 to 27.0.

[0046]

[16] The thermoplastic resin according to any one of [1] to

[15] above, wherein the thermoplastic resin has a Tg of 105 to 170°C.

[0047]

[17] A molded article comprising the thermoplastic resin according to any one of [1] to

[16] above.

[0048]

[18] The molded article according to

[17] above, wherein the molded article is an optical lens or an optical film.

[0049] Effects of the Invention

[0050] According to the present invention, it is possible to realize a thermoplastic resin having excellent properties such as a high refractive index and an Abbe number, and a molded product such as an optical lens containing such a thermoplastic resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is a graph showing the relationship between the Abbe number and the refractive index of the thermoplastic resins of Examples 1 to 5 and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0052] The thermoplastic resin of the present invention has at least the structural unit represented by the general formula (1).

[0053]

[0054] The structural unit of the general formula (1) contains -OSi(R 1 R 2 )O-site silane structural unit (S) and the diol structural unit (A) derived from a dihydroxy compound represented by M in the formula.

[0055] Examples of the thermoplastic resin include polycarbonate resins, polyester resins, and polyester carbonate resins.

[0056] The silane structural unit (S) in the thermoplastic resin is a structural unit derived from, for example, a dialkoxysilane compound having a naphthyl group. The diol structural unit (A) is derived from a diol compound described in detail below. The thermoplastic resin is described in detail below.

[0057] [I. Thermoplastic resin]

[0058] <I-1. Types of structural units>

[0059] (1) Silane structural unit (S)

[0060] The silane structural unit (S) in the thermoplastic resin is a structural unit containing a silyl ether bonding site of the above formula (1), that is, containing -OSi(R 1 R 2 )O-site structural unit. In addition, in the silane structural unit (S), R 1 and R 2 At least one of the groups is a polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent.

[0061] The type of silane compound used for the polymerization of such thermoplastic resin can be appropriately selected according to the type of silane structural unit (S) formed on the main chain. The silane structural unit (S) acts as a connecting group connected to the diol structural unit (A), and the silane compound used to form the silane structural unit (S) is also referred to as a linking agent below.

[0062] In the above formula (1), R 1 and R 2 At least one of the polycyclic aryl groups is a polycyclic aryl group having 10 to 30 carbon atoms, and the polycyclic aryl group may have a substituent. The polycyclic aryl group which may have a substituent preferably has 10 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, and further preferably 10 to 16 carbon atoms.

[0063] In the silane structural unit (S), R 1 and R 2 Preferably, each is independently selected from a polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent. 1 and R 2 All are preferably polycyclic aromatic groups which may have a substituent.

[0064] Examples of the aromatic ring in the polycyclic aromatic group of the silane structural unit (S) include a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyrene ring, a perylene ring, a triphenylene ring (triphenylene ring), a tetracene ring (naphthonaphthylene ring), Ring, fluorene ring, acenaphthacene ring, fluoranthene ring, etc.

[0065] Therefore, as R in the silane structural unit (S), 1 or R 2 Specific examples of the polycyclic aromatic group include naphthyl, phenanthrenyl, anthracenyl, pyrenyl, perylenyl, triphenylenyl, tetraphenylene (naphthonaphthyl), fluorenyl, acenaphthenyl, fluoranyl, etc.

[0066] R in the silane structural unit (S) 1 or R 2 The polycyclic aromatic group is preferably a condensed polycyclic aromatic group including a condensed ring, more preferably has a structure in which 2 to 4 benzene rings are condensed, and further preferably has a structure in which 2 to 3 benzene rings are condensed.

[0067] As R in the silane structural unit (S) 1 and R 2 Preferred specific examples of the above include naphthyl containing a naphthalene ring, phenanthryl containing a phenanthrene ring, anthracenyl containing anthracene ring, pyrenyl containing a pyrene ring, triphenylene containing a triphenylene ring, naphthyl containing a tetraphenylene ring, and tetraphenylene containing a tetraphenylene ring. Ring Ji et al.

[0068] The aromatic ring constituting the polycyclic aromatic group in the silane structural unit (S) may be bonded to the Si atom at any position.

[0069] For example, the polycyclic aromatic group containing a naphthalene ring is 1-naphthyl, 2-naphthyl, etc., the polycyclic aromatic group containing an anthracene ring is 1-anthryl, 2-anthryl, 9-anthryl, etc., the polycyclic aromatic group containing a phenanthrene ring is 1-phenanthryl, 2-phenanthryl, 9-phenanthryl, etc., the polycyclic aromatic group containing a pyrene ring is 1-pyrene, 9-pyrene, 10-pyrene, etc., the polycyclic aromatic group containing a triphenylene ring is 1-triphenylene, 1-naphthyl, 1-tetraphenylene, 1- Base, 4- Base or 12- Among these specific examples, 1-naphthyl, 2-naphthyl, 9-phenanthryl, etc. are preferably used as R 1 or R 2 That is, R 1 and R 2 Preferably, they are each independently selected from a naphthyl group which may have a substituent, such as 1-naphthyl and 2-naphthyl, and a phenanthrenyl group which may have a substituent, such as 9-phenanthrenyl.

[0070] In the structural unit of formula (1), R other than the polycyclic aromatic group 1 and R other than polycyclic aromatic groups 2 Preferably, each of them is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a monocyclic aryl group having 6 to 30 carbon atoms which may have a substituent.

[0071] R other than the polycyclic aromatic group in the silane structural unit (S) 1 or R 2 In the case of a monocyclic aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, the total number of carbon atoms is more preferably 6 to 12, and the total number of carbon atoms is particularly preferably 6 to 8.

[0072] In addition, R other than the polycyclic aromatic group in the silane structural unit (S) 1 or R 2 In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 14 or 1 to 10, the total number of carbon atoms is more preferably 1 to 6, and the total number of carbon atoms is particularly preferably 1 or 2.

[0073] In addition, as R 1 and R 2 Preferred specific examples other than the polycyclic aryl group of include phenyl, benzyl, methyl, methyl, propyl and the like, and more preferred is a phenyl group which may have a substituent.

[0074] Examples of the substituent in the silane structural unit (S) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidyloxy, and mercapto. 1 or R 2 When it is an aryl group, it may contain an alkyl group as a substituent. 1 or R 2 In the case of an alkyl group, an aryl group may be contained as a substituent.

[0075] In addition, in the 1 or R 2 In other words, when the silane structural unit (S) contains a substituent, the above-mentioned carbon number also includes the carbon number of the substituent. In other words, when the silane structural unit (S) contains a substituent, the above-mentioned range of carbon atoms is the total number of carbon atoms including the carbon number of the substituent.

[0076] In thermoplastic resins, the total number of R 1 and R 2 The ratio of the polycyclic aromatic group that may contain a substituent is preferably 30 mol% or more, based on the total molar number of . The ratio of the polycyclic aromatic group that may contain a substituent in all the silane structural units (S) of the thermoplastic resin is more preferably 40 mol% or more or 50 mol% or more, further preferably 60 mol% or more or 70 mol% or more, particularly preferably 80 mol% or more, 90 mol% or more or 95 mol% or more.

[0077] In the thermoplastic resin, based on the total number of moles of the silane structural unit (S), R in the formula (1) 1 and R 2 The ratio of silane structural units which are all polycyclic aromatic groups which may have a substituent is preferably 30 mol% or more. 1 and R 2 The proportion of structural units which are all polycyclic aromatic groups which may contain substituents is more preferably 40 mol% or 50 mol% or more, further preferably 60 mol% or 70 mol% or more, particularly preferably 80 mol% or more, 90 mol% or more, or 95 mol% or more.

[0078] The silane compound for forming the silane structural unit (S) is preferably selected from dialkoxysilane compounds, diaryloxysilane compounds and monoalkoxymonoaryloxysilane compounds, which are compounds each containing a polycyclic aromatic group which may have at least one substituent.

[0079] The dialkoxysilane compound includes at least any one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane.

[0080] The diaryloxysilane compound includes at least any one of dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane.

[0081] The monoalkoxymonoaryloxysilane compound includes at least any one of a dialkylmonoalkoxymonoaryloxysilane, a diarylmonoalkoxymonoaryloxysilane, and a monoalkylmonoarylmonoalkoxymonoaryloxysilane compound.

[0082] The silane compound used to form the silane structural unit (S) is preferably of the general formula Si(R 1 R 2 )(OR 3 ) 2 Indicates that R 1 and R 2 As mentioned above. The general formula of silane compounds is Si(R 1 R 2 )(OR 3 ) 2 OR 3 The groups each independently represent an alkoxy group or an aryloxy group. The two -OR 3 The group may not be a group introduced into the polymer chain (main chain) of the thermoplastic resin, but may be a group that produces byproducts such as methanol and phenol (MeOH, PhOH). Therefore, there is no particular limitation on the type of alkoxy or aryloxy group. Among them, in order to remove the byproducts in the polymerization process from the reaction system as easily as possible, aryloxy and alkoxy groups with relatively small carbon atoms are preferred, for example, aryloxy groups with less than 8 carbon atoms or alkoxy groups with less than 3 carbon atoms are preferred, and phenoxy (-OC 6 H 5 1-3, 1-dioxygen), 1-dioxygen, ...

[0083] Preferred specific examples of silane compounds for forming the silane structural unit (S) include naphthylalkyldialkoxysilane, dinaphthyldialkoxysilane represented by the following formula (1-1a), naphthylalkylalkoxyphenoxysilane, dinaphthylalkoxyphenoxysilane, naphthylalkyldiphenoxysilane, dinaphthyldiphenoxysilane, etc. More preferred specific examples of silane compounds include dinaphthyldialkoxysilanes such as di(1-naphthyl)dimethoxysilane, di(1-naphthyl)diethoxysilane, di(2-naphthyl)dimethoxysilane, and di(2-naphthyl)diethoxysilane.

[0084]

[0085] In formula (1-1a), R each independently represents an alkyl group which may have a substituent, and the number of carbon atoms of the alkyl group is, for example, any one of 1 to 6, preferably any one of 1 to 4, and more preferably 1 or 2. Specific examples of the substituent are as described above.

[0086] In addition, any one or all of the naphthyl groups in the silane compound represented by the above formula (1-1a) may be replaced by phenyl, alkyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, triphenylenyl, naphthacene (naphthyl), Compounds substituted with acenaphthenyl, fluorenyl, acenaphthacenyl, or fluoranthenyl can also be preferred specific examples of the silane compound.

[0087] The silane compound is, for example, (mononaphthyl)phenyldialkoxysilane represented by the following formula (1-1b), (monophenanthryl)phenyldialkoxysilane represented by the following formula (1-1c), etc. It can be (mononaphthyl)alkyldialkoxysilane, (monophenanthryl)alkyldialkoxysilane, (mononaphthyl)phenyldiaryloxysilane, (monophenanthryl)phenyldiaryloxysilane, etc.

[0088]

[0089] In formula (1-1b) and formula (1-1c), R each independently represents an alkyl group which may have a substituent, and the number of carbon atoms of the alkyl group is, for example, any one of 1 to 6, preferably any one of 1 to 4, and more preferably 1 or 2. Specific examples of the substituent are as described above.

[0090] In addition, as described above, the thermoplastic resin may contain -OSi(R 1 R 2 )O-part, R 1 and R 2 All of them are structural units that are not polycyclic aromatic groups. As silane compounds for forming such structural units, silane compounds having a phenyl group which may have a substituent are preferred, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. are preferred.

[0091] As the silane compound constituting the structural unit such as the silane structural unit (S), a single type of dialkoxysilane compound may be used, or a plurality of types of dialkoxysilane compounds may be used in combination.

[0092] (2) Diol structural unit (A)

[0093] In the above formula (1), M, which is simply represented, is a diol structural unit (A) derived from a dihydroxy compound. The diol structural unit (A) includes a structural unit (B) derived from a prescribed diol including bisphenols, a binaphthyl structural unit (N), a fluorene structural unit (F), and the like. Most of the diol structural units (A) are combined with silane structural units at their ends, and a part of the diol structural units (A) may be combined with each other between the diol structural units (A). The diol structural unit (A) is described in detail below.

[0094] (2-1) Structural unit derived from bisphenols (bisphenol structural unit (B))

[0095] For example, the structural unit (B) derived from a diol such as bisphenols is represented by any of the following formulae (A-1) and (A-2).

[0096]

[0097] (In formulas (A-1) and (A-2), R 3 ~R 10 and R 30 ~R 33 Each of them is independently hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

[0098] R 3 ~R 10 and R 30 ~R 33 In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, the total number of carbon atoms is more preferably 1 to 4, and the total number of carbon atoms is particularly preferably 1 or 2.

[0099] R 3 ~R 10 and R 30 ~R 33 In the case of an alkenyl group which may have a substituent, the total number of carbon atoms is preferably 2 to 10, the total number of carbon atoms is more preferably 2 to 6, and the total number of carbon atoms is particularly preferably 2 to 4.

[0100] In addition, R 3 ~R 10 and R 30 ~R 33 In the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, the total number of carbon atoms is more preferably 6 to 12, and the total number of carbon atoms is particularly preferably 6 to 8.

[0101] Z 1 and Z 2Each of Z is independently an alkylene group having 1 to 5 carbon atoms which may have a substituent. 1 and Z 2 Each of them is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms.

[0102] In formulas (A-1) and (A-2), J 1 and K 1 Each independently represents an integer from 0 to 5. 1 and K 1 Each of them is preferably an integer of 0 or more and 3 or less, more preferably an integer of 1 or more and 3 or 0 or more and 2 or less, and 1 or 2 is particularly preferred, for example.

[0103] In addition, in J 1 and K 1 When both are 1 or more, the structural unit (B) is preferably derived from a dihydroxy compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group.

[0104] For example, it is preferred that -OZ bonded to the cyclic skeleton via the formula (A-1) and (A-2) 1 -and-OZ 2 - The parts are independently 2 OH, -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 The structural unit (B) is formed by a dihydroxy compound substituted with an alkyl group having 1 to 5 carbon atoms and having a hydroxyl group at the terminal (alkyl group in which the terminal hydrogen is substituted with a hydroxyl group) such as OH.

[0105] In addition, the compounds of formula (A-1) and (A-2) which do not have a cyclic skeleton and contain -CH 2 OH, -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 An aliphatic dihydroxy compound having an alkyl group having a terminal hydroxyl group (an alkyl group in which the terminal hydrogen is substituted by a hydroxyl group) and having a carbon number of 1 to 5 such as OH is used in combination with the above-mentioned aromatic dihydroxy compound to form the structural unit (B). Alternatively, a structural unit replacing the structural unit (B) may be formed using only such an aliphatic dihydroxy compound.

[0106] The number of carbon atoms in the alkyl group having a terminal hydroxyl group is preferably 1 or more and 3 or less, and more preferably 1 or 2.

[0107] In formulae (A-1) and (A-2), X is independently a single bond or any of the structural formulae represented by the following formula (2).

[0108]

[0109] In formula (2), R 11 and R 12 Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or is R 11 and R 12 They are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms which may have a substituent.

[0110] a and b each independently represent 0 or an integer from 1 to 5000.

[0111] R 11 and R 12 Preferably, each of them independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent.

[0112] In formula (2), a and b are each independently an integer of 0 or 1 and 5000 or less, and a and b are preferably an integer of 1000 or less, more preferably an integer of 500 or less, and further preferably an integer of 100 or less.

[0113] In addition, in the siloxane structural unit, X is preferably R 11 and R 12 The fluorene ring structure formed by mutual combination.

[0114] Examples of the substituent in the structural unit (B) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidyloxy, mercapto, etc. When the structural unit (B) contains a substituent, the above range of carbon atoms is the total number of carbon atoms including the carbon atoms of the substituent.

[0115] Specific examples of the structural unit (B) include structural units derived from bisphenol compounds, such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol C, bisphenol BP, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, etc.

[0116] (2-2) Binapthyl structural unit (N)

[0117] The binaphthyl structural unit (N) is preferably derived from a binaphthyl-containing dihydroxy compound. The binaphthyl-containing dihydroxy compound used to form the binaphthyl structural unit (N) is preferably selected from compounds represented by the following formula (3).

[0118]

[0119] In the general formula (3), Ra and Rb are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and containing one or more heteroatoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-Rh. Rh represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and containing one or more heteroatoms selected from O, N and S and which may have a substituent.

[0120] Ra and Rb are preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N and S and may have a substituent. They are more preferably a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may have a substituent, and further preferably a hydrogen atom or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0121] In the general formula (3), X represents a single bond or a fluorenyl group which may have a substituent. X is preferably a single bond or a fluorenyl group which may have a substituent and has a total carbon number of 12 to 20.

[0122] In the general formula (3), A and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms.

[0123] In the general formula (3), m and n are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.

[0124] In the general formula (3), a and b are each independently an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0125] Examples of the substituent in the above-mentioned binaphthyl structural unit (N) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidyloxy, mercapto, etc. When the binaphthyl structural unit (N) contains a substituent, the above-mentioned range of carbon atoms is the total number of carbon atoms including the carbon number of the substituent.

[0126] Specific examples of the binaphthyl structural unit (N) include structural units derived from 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (DPBN), 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl (2NBN), 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE), etc. More preferred are structural units derived from 2NBN, DPBN, etc.

[0127] As described above, the thermoplastic resin containing the binaphthyl structural unit (N) has been confirmed to have a higher heat resistance effect than the thermoplastic resin containing the structural unit containing an alicyclic ring derived from an alicyclic diol, the structural unit containing a monocyclic aromatic ring derived from bisphenols, etc.

[0128] (2-3) Fluorene structural unit (F)

[0129] The fluorene structural unit (F) is derived from a fluorene ring-containing dihydroxy compound. The fluorene ring-containing dihydroxy compound is preferably a compound represented by the following general formula (3), for example.

[0130]

[0131] In the general formula (4), Rc and Rd are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0132] Rc and Rd are preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N and S and may have a substituent, more preferably a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may have a substituent, and still more preferably a hydrogen atom or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0133] In the general formula (4), Y 1 At least one fluorene group which may have a substituent. 1 In addition to the fluorene structural unit (F) which is a fluorene group which may have a substituent, Y 1 Different fluorene structural units. That is, in the general formula (4), Y 1 It may be a single bond or any of the structural formulas represented by the following formulas (8) to (14), and is preferably a fluorenyl group, a single bond, or a structural formula represented by the following formula (8).

[0134]

[0135] In formulas (8) to (14), R 61 , R 62 , R 71 and R 72 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, or represents R 61 and R 62 , or R 71 and R 72 They are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms which may have a substituent.

[0136] In formulas (8) to (14), r and s are each independently an integer of 0 to 5000.

[0137] In the above general formula (4), A and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the above general formula (4), p and q are each independently an integer of 0 to 4, and preferably 0 or 1. In addition, in the above general formula (4), a and b are each independently an integer of 0 to 10, and preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0138] Examples of the substituent in the fluorene structural unit (F) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidyloxy, mercapto, etc. When the fluorene structural unit (F) contains a substituent, the above range of carbon atoms is the total number of carbon atoms including the carbon atoms of the substituent.

[0139] Specific examples of the fluorene structural unit (F) include BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclododecylenebisphenol), bisphenol P-HTG (4,4'-( 3,3,5-trimethylcyclohexyl)bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylene)bisphenol), bisphenol PEO-FL (bisphenoxyethanol fluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol),) TrisP-HAP (4,4',4"-ethylidenetriphenol), etc.

[0140] Among these, more preferred specific examples of the fluorene structural unit (F) include structural units derived from BNEF, BPEF or BPPEF.

[0141] In addition, the fluorene ring-containing dihydroxy compound as a compound for forming the fluorene structural unit (F) is also described as component A below, and the binaphthyl-containing dihydroxy compound as a compound for forming the above-mentioned binaphthyl structural unit (N) is also described as component B below.

[0142] When component B is used together with component A and copolymerized, a thermoplastic resin having a high refractive index can be obtained. In addition, in the thermoplastic resin produced using component B, a low molecular weight body described in detail later can be easily contained only in an appropriate amount. It can be considered that such a thermoplastic resin has the advantages of improved plasticity during molding, improved productivity, and reduced energy consumption.

[0143] (2-4) Any structural unit (structural unit (Z))

[0144] The thermoplastic resin may contain structural units (arbitrary structural units (Z)) other than the silane structural unit, which is called the main component, the prescribed diol structural unit (B), the binaphthyl structural unit (N) and the fluorene structural unit (F) constituting the main chain, for example, structural units derived from the following diol compounds.

[0145] Examples of the structural unit (Z) that the thermoplastic resin may contain include the following: 1 )~(I 6 ) are structural units of diol compounds represented by any one of the above. These diol compounds are sometimes referred to as diol compounds (I 1 )~(I 6 ).

[0146] Diol compound (I 1 ) is represented by the following formula (I 1 )express.

[0147]

[0148] [Wherein,

[0149] R 1 and R 2 Independently expressed - (CR 5 R 6 ) q1 -or-(-O-(CR 5 R 6 ) q2 -) q3 -(where R 5 and R 6 Independently represents H or C 1-6 alkyl, q1 represents an integer of 0 to 10, q2 represents an integer of 1 to 10, q3 represents an integer of 1 to 10, and when q1 or q2 is an integer of 2 or more, multiple R 5 or R 6 may be the same or different from each other),

[0150] R 3 and R 4 independently represents one or more halo groups selected from chlorine, bromine and iodine, C 1-20 Aliphatic hydrocarbon group, C 1-20 Alkoxy, C 3-20 Cycloalkyl, C 6-20 Aromatic hydrocarbon group, C 7-20 Aralkyl, C 6-20 Aromatic oxyalkyl, or C 3-20 Cycloalkoxy,

[0151] X 1is any of the following groups,

[0152]

[0153] (Where,

[0154] R 7 and R 8 independently represent H, one or more halogeno groups selected from chlorine, bromine and iodine, C 1-20 an aliphatic hydrocarbon group, a C 1-20 Alkoxy, optionally substituted C 6-20 Aromatic hydrocarbon group, or R 7 and R 8 Can combine to form C 3-20 Carbocyclic ring or 5-12 membered heterocyclic ring,

[0155] R 9 and R 10 Independently represents H or C 1-6 Alkyl, when r1 is an integer greater than 2, multiple R 9 or R 10 They can be the same or different from each other.

[0156] R 11 ~R 18 independently represents one or more halogenated groups selected from chlorine, bromine and iodine, and C 1-20 an aliphatic hydrocarbon group, a C 1-20 Alkoxy, or C optionally substituted 6-12 Aromatic hydrocarbon groups,

[0157] R 19 represents a C that may have a substituent α 1-9 Alkylene,

[0158] r1 represents an integer greater than or equal to 1 and less than or equal to 20,

[0159] r2 represents an integer greater than or equal to 1 and less than or equal to 500. )

[0160] The above formula (I 1 )middle,

[0161] p1 and p2 independently represent an integer greater than or equal to 0 and less than or equal to 4,

[0162] The substituent α is selected from C 1-6 Alkoxy, C 1-7 an acyl group, one or more halide groups selected from chlorine, bromine and iodine, an amino group, a nitro group, a cyano group and one or more substituents selected from carbamoyl groups,

[0163] The substituent β is selected from C1-6 Alkyl, C 1-6 Alkoxy, C 1-7 an acyl group, one or more halogeno groups selected from the group consisting of chlorine, bromine and iodine, and one or more substituents selected from the group consisting of amino, nitro, cyano and carbamoyl.

[0164] When the diol compound contains a substituent, the range of the number of carbon atoms refers to the total number of carbon atoms including the number of carbon atoms of the substituent.

[0165] As the above formula (I 1 ) 1 and R 2 The option of - (CR 5 R 6 ) q1 -, for example, ethylene (-CH 2 CH 2 -), as -O-(CR 5 R 6 ) q2 - For example, -O-CH 2 CH 2 - and -O-CH(CH 3 )CH 2 -. In addition, R 1 CR 5 R 6 ) q2 -) q3 From the perspective of stability, HO-R 1 -Ph is not HO-(-O-(CR 5 R 6 ) q2 -) q3 -Ph, and HO-(-(CR 5 R 6 ) q2 -O-) q3 -Ph. q2 is preferably 2 or more.

[0166] Examples of the "halogeno group" include chlorine, bromine and iodine, preferably chlorine or bromine, and more preferably chlorine.

[0167] “C 1-20 The term "aliphatic hydrocarbon group" refers to a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include C 1-20 Alkyl, C 2-20 Alkenyl, and C 2-20 Alkynyl. As C 1-20Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, and n-eicosyl. 1-10 Alkyl or C 1-6 Alkyl, more preferably C 1-4 Alkyl or C 1-2 Alkyl, more preferably methyl. 2-20 Examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and the like. Preferably, C 2-10 Alkenyl or C 2-6 The alkenyl group is more preferably vinyl (Ethenyl, vinyl) or 2-propenyl (allyl). 2-20 Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, and eicosynyl. 2-10 Alkynyl or C 2-6 Alkynyl, more preferably C 2-4 Alkynyl or C 2-3 Alkynyl.

[0168] “C 1-20 "Alkoxy" refers to a linear or branched monovalent aliphatic hydrocarbon oxy group having 1 to 20 carbon atoms. For example, it is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, etc., preferably C 1-10 Alkoxy or C 1-6 Alkoxy, more preferably C 1-4 Alkoxy or C 1-2 The alkoxy group is more preferably a methoxy group.

[0169] “C 3-20 "Cycloalkyl" refers to a monovalent cyclic saturated aliphatic hydrocarbon group having 3 or more and 20 or less carbon atoms. For example, it is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Preferably, C 3-10 Cycloalkyl.

[0170] “C 6-20 The "aromatic hydrocarbon group" refers to a monovalent aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms. For example, phenyl, indenyl, naphthyl, biphenyl, acenaphthenyl, fluorenyl, phenalenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, phenyl, tetraphenyl, peryl, etc., preferably C6-12 The aromatic hydrocarbon group is more preferably a phenyl group.

[0171] “C 7-20 The term "aralkyl" refers to an alkyl group substituted with one aromatic hydrocarbon group, and has 7 to 20 carbon atoms. Examples thereof include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and biphenylmethyl, and benzyl is preferred.

[0172] “C 6-20 The term "aromatic hydrocarbonoxy group" refers to a monovalent aromatic hydrocarbonoxy group having 6 or more and 20 or less carbon atoms. For example, it is phenoxy, indenyloxy, naphthyloxy, biphenyloxy, acenaphthyloxy, fluorenyloxy, phenanthrenyloxy, phenanthrenyloxy, anthracenyloxy, anthracenyloxy, triphenylenyloxy, pyreneoxy, Oxy, naphthyloxy, peryloxy, etc., preferably C 6-12 The aromatic hydrocarbonoxy group is more preferably a phenoxy group.

[0173] “C 3-20 "Cycloalkoxy" refers to a monovalent cyclic saturated aliphatic hydrocarbon group having 3 or more and 20 or less carbon atoms. For example, it is cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, cyclododecyl, etc. Preferably, C 3-12 Cycloalkoxy.

[0174] As the substituent α, there can be mentioned those selected from C 1-6 Alkoxy, C 1-7 an acyl group, one or more halogeno groups selected from the group consisting of chlorine, bromine and iodine, and one or more substituents selected from the group consisting of amino, nitro, cyano and carbamoyl.

[0175] As the substituent β, there can be mentioned those selected from C 1-6 Alkyl, C 1-6 Alkoxy, C 1-7 an acyl group, one or more halogeno groups selected from the group consisting of chlorine, bromine and iodine, and one or more substituents selected from the group consisting of amino, nitro, cyano and carbamoyl.

[0176] In the “amino group”, except for the unsubstituted amino group (-NH 2 ) and 1 C 1-6 Alkyl substituted single C 1-6 Alkylamino and 2 C 1-6 Alkyl substituted di-C 1-6 As such an amino group, there can be mentioned amino group (—NH 2 ); methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, n-pentylamino, n-hexylamino and the like mono-C 1-6Alkylamino; dimethylamino, diethylamino, di(n-propyl)amino, diisopropylamino, di(n-butyl)amino, diisobutylamino, di(n-pentyl)amino, di(n-hexyl)amino, ethylmethylamino, methyl(n-propyl)amino, n-butylmethylamino, ethyl(n-propyl)amino, n-butylethylamino, etc. 1-6 Alkylamino group is preferably an unsubstituted amino group.

[0177] “C 1-7 The term "acyl group" refers to an atomic group remaining after removing OH from an aliphatic carboxylic acid having 1 or more and 7 or less carbon atoms. For example, it is formyl, acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, tert-butylcarbonyl, n-pentylcarbonyl, n-hexylcarbonyl, etc., preferably C 1-4 The acyl group is more preferably an acetyl group.

[0178] The number of substituents of the substituent α is not particularly limited as long as they can be substituted, and can be, for example, 1 or more and 20 or less. The number of substituents is preferably 10 or less, more preferably 5 or less or 3 or less, and further preferably 2 or less or 1.

[0179] The number of substituents of the substituent β is not particularly limited as long as they can be substituted, and can be, for example, 1 or more and 10 or less. The number of substituents is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less or 1.

[0180] As R 7 and R 8 C 5-20 Carbon rings, including C 3-20 Cycloalkyl groups and condensed rings of cycloalkyl groups and aromatic hydrocarbon groups. Examples of such condensed rings include acenaphthenyl and fluorenyl.

[0181] As R 7 and R 8 Examples of the 5- to 12-membered heterocyclic ring formed by the combination include oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, oxathiolanyl, piperidinyl, and 1(3H)-isobenzofuranonyl.

[0182] As diol compound (I 1 ), specifically, the following compounds can be mentioned.

[0183] For example, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,ω-bis[3-(o-hydroxyphenyl)] )propyl] polydimethyldiphenyl random copolymer siloxane, α, ω-bis[3-(o-hydroxyphenyl)propyl] polydimethylsiloxane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-( 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 4-(9-(4-hydroxyethoxy)phenyl)-9H-fluoren-9-yl)phenol, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 4,4-bis(2-hydroxyethoxy)biphenyl, 2,2'(9H-fluoren-9,9'-diyl)bis(ethane-1-ol), 9H-fluoren-9,9-diyl)dimethanol, 2,2'-(1,4-phenylene)bis(ethane-1-ol), 2,2'-(1,4-phenylene)bis(methane-1-ol), 2,2'-(1,4-phenylenebis(oxy))bis(ethane-1-ol), 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-sec-butylphenyl)cyclododecane phenyl)cyclododecane, 1,1-bis(4-hydroxy-3-allylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-fluorophenyl)cyclododecane, 1,1-bis(4-hydroxy-3-chlorophenyl)cyclododecane, 1,1-bis(4-hydroxy-3-bromophenyl)cyclododecane, 7-ethyl-1,1-bis(4-hydroxyphenyl)cyclododecane, 5,6-dimethyl-1,1-bis(4-hydroxyphenyl)cyclododecane.

[0184] Among these, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 1,1-bis(4-hydroxyphenyl)cyclododecane, and 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane are particularly preferred. Representative diol compounds (I) are shown below. 1 ).

[0185]

[0186] [Where R 1 and R 2 Means the same as above.]

[0187] However, depending on the circumstances, the diol compound (I 1 ) may not include bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, and bisphenol Z.

[0188] Diol compound (I 2 ) as shown in the following formula (I 2 ) as shown.

[0189]

[0190] [Where R 1 and R 2 Means the same as above, X2 With X 1 Meaning the same thing.]

[0191] As diol compound (I 2 ), specifically, 9,9-bis[6-(1-hydroxymethoxy)naphth-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphth-2-yl]fluorene, and 9,9-bis[6-(4-hydroxybutoxy)naphth-2-yl]fluorene. Among them, 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene is preferred.

[0192] Diol compound (I 3 ) as shown in the following formula (I 3 ) as shown.

[0193] HO-R 1 -X 3 -R 2 -OH(I 3 )

[0194] [Where R 1 and R 2 Means the same as above, X 3 Represents C 15-32 Divalent aromatic hydrocarbon group.]

[0195] As C 15-32 Examples of the divalent aromatic hydrocarbon group include fluoranthenylene, acephenanthrylenylene, aceantrylenylene, triphenylene, pyrenylene, C, such as phenylene, tetraphenylene, heptahedralene, picenylene, perylenylene, biphenylene, pentaphenylene, pentaphenylene, tetra-o-phenylene, hexaphenylene, hexaphenylene, rubidinyl, coronaphenylene, trinaphthylene, heptaphenylene, heptahedralene, pyranthrylene, ovarenylene, etc. 15-32 Divalent condensed polycyclic aromatic hydrocarbon group; terphenylene, quaterphenylene, etc.

[0196] X 3 R 3 The number of the groups is not particularly limited as long as they can be substituted, and can be, for example, 1 or more and 10 or less, preferably 8 or less or 5 or less, and more preferably 1 or 2.

[0197] As diol compound (I3 ), specifically, the binaphthylene glycol compound represented by the following formula can be mentioned.

[0198]

[0199] [Where R 1 and R 2 Means the same as above.]

[0200] Examples of such binaphthyl diol compounds include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, and 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred.

[0201] Diol compound (I 4 ) as shown in the following formula (I 4 ) as shown.

[0202] HO-R 20 -X 4 -R 21 -OH(I 4 )

[0203] [Wherein,

[0204] R 20 and R 21 Independent representation - (CR 5 R 6 ) m1 -or-(-O-(CR 5 R 6 ) m2 -) m3 -(where R 5 and R 6 Means the same as above, m 1 represents an integer greater than or equal to 1 and less than or equal to 10, m 2 represents an integer greater than or equal to 1 and less than or equal to 10, m 3 represents an integer greater than or equal to 1 and less than or equal to 10, m 1 or m 2 When the integer is 2 or more, multiple R 5 or R 6 may be the same or different from each other),

[0205] X 4 It represents a divalent group containing one or more hydrocarbon rings or heterocyclic rings.]

[0206] As m 2, preferably 2 or more.

[0207] As the above formula (I 4 ) 20 and R 21 The option of - (CR 5 R 6 ) m1 -, for example, ethylene (-CH 2 CH 2 -), as -O-(CR 5 R 6 ) m2 -, for example, -O-CH 2 CH 2 - and -O-CH(CH 3 )CH 2 -. In addition, R 1 CR 5 R 6 ) m2 -) m3 From the perspective of stability, HO-R 1 -X 3 -Not HO-(-O-(CR 5 R 6 ) m2 -) m3 -X 3 -, and HO-(-(CR 5 R 6 ) m2 -O-) m3 -X 3 -

[0208] Examples of the divalent group containing one or more hydrocarbon rings or heterocyclic rings include divalent C 6-32 Aromatic hydrocarbon group, divalent C optionally substituted 3-20 Cycloalkyl, divalent C 6-32 An aromatic hydrocarbon group and a divalent C 3-20 A divalent radical of a cycloalkyl group.

[0209] Bivalent C 6-32 The aromatic hydrocarbon group may contain a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as long as it exhibits aromaticity as a whole. 6-32 The aromatic hydrocarbon group is not particularly limited, and examples thereof include the following groups.

[0210]

[0211] Bivalent C 3-20The cycloalkyl group may contain a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom.

[0212] As a divalent C 3-14 The cycloalkyl group is not particularly limited, and examples thereof include the following groups.

[0213]

[0214] As each of the divalent C 6-32 An aromatic hydrocarbon group and a divalent C 3-20 The divalent group of the cycloalkyl group is not particularly limited, and examples thereof include the following groups.

[0215]

[0216] Diol compound (I 5 ) as shown in the following formula (I 5 ) as shown.

[0217] HO-R 1 -X 5 -R 2 -OH(I 5 )

[0218] [Where R 1 and R 2 Means the same as above, X 5 represents a divalent saturated heterocyclic group.]

[0219] The divalent saturated heterocyclic group is not particularly limited, and the following groups can be mentioned.

[0220]

[0221] Diol compound (I 6 ) as shown in the following formula (I 6 ) as shown.

[0222]

[0223] [Wherein, X 6 Represents C 1-10 Alkylene,

[0224] n represents an integer greater than or equal to 13 and less than or equal to 50.]

[0225] C 1-10 The alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. 2 -、-CH 2 CH 2 -、-CH 2CH 2 CH 2 -、-CH 2 CH(CH 3 )-、-CH(CH 3 )CH 2 -、-CH 2 CH 2 CH 2 CH 2 -. Diol compound (I 6 ) 6 They can be the same or different. There are multiple X 5 When -O-X 6 The arrangement of - can be random or block-like. 1-10 Alkylene, preferably C 2-10 Alkylene.

[0226] Only one diol compound may be used alone, or two or more diol compounds may be used in combination. For example, by using two or more diol compounds in combination, copolymerized polycarbonate can be well produced. However, from the viewpoint of production efficiency, it is preferred to use only one diol compound alone. When two or more diol compounds are used, the number of diol compounds is preferably 5 or less, more preferably 3 or less, and further preferably 2. By using two or more diol compounds and copolymerizing them by the method of the present invention, the physical property range of the obtained polycarbonate is wide, and it is easy to adjust the physical properties.

[0227] About C 1-4 The amount of the halogenated hydrocarbon and the diol compound used is not particularly limited as long as the reaction proceeds and the desired product can be obtained. 1-4 The above reaction also proceeds when the molar number of the halogenated hydrocarbon is 1 times the molar number of the diol compound. In addition, from the viewpoints of reaction efficiency and reaction time, it is preferred to increase the diol compound relative to C 1-4 The molar ratio of halogenated hydrocarbons ([diol compound] / [C 1-4 The molar ratio is preferably 0.01 or more, more preferably 0.1 or more, and more preferably 0.8 or less, more preferably 0.5 or less. When the molar ratio is too large, the amount of the compound containing the nucleophilic functional group increases relatively, and thus the amount of the unreacted compound containing the nucleophilic functional group increases. On the other hand, when the molar ratio is too small, the amount of the unreacted C 1-4 The increase of halogenated hydrocarbons may lead to the release of carbonyl halides outside the reaction system. 1-4 Halogenated hydrocarbons are liquid at room temperature and pressure and can also be used as solvents. 1-4The ratio of the halogenated hydrocarbon is set to 1 mg / mL or more and 500 mg / mL or less.

[0228] Among the above-mentioned arbitrary structural units (Z), structural units derived from diols having an aromatic ring which tends to increase the refractive index value of the thermoplastic resin are preferred. In addition, structural units derived from aliphatic hydroxyl groups (e.g., -CH 2 Based on the above, it is preferably a structural unit of a diol of the general formula (I) containing an aromatic ring and an aliphatic hydroxyl group. 1 )~(I 3 ) shown in the diol compound (I 1 )~(I 3 )'s structural unit (Z).

[0229] The thermoplastic resin may be a random copolymer or a block copolymer consisting only of a silane structural unit, a binaphthyl structural unit (N) and a fluorene structural unit (F). In addition, the thermoplastic resin may be any one of a random copolymer or a block copolymer containing a silane structural unit, a binaphthyl structural unit (N), a fluorene structural unit (F) and a structural unit (Z).

[0230] In addition, the thermoplastic resin is preferably a random copolymer from the viewpoint of the properties of the thermoplastic resin, simplification of the production process, etc. In addition, the number of combinations of the binaphthyl structural units (N) via the silane structural unit and the number of combinations of the fluorene structural units (F) via the silane structural unit are as small as possible, and it is preferred that a large number of the binaphthyl structural units (N) and the fluorene structural units (F) are alternately combined via the silane structural unit.

[0231] In the thermoplastic resin, the above-mentioned structural units, i.e., the silane structural unit, the binaphthyl structural unit (N), the fluorene structural unit (F) and the arbitrary structural unit (Z) are preferably bonded via an ether bond, and more preferably, substantially all structural units in the thermoplastic resin are bonded via an ether bond.

[0232] However, a carbonate bond and / or an ester bond may exist in the thermoplastic resin, and the thermoplastic resin may be a polycarbonate resin, a polyester resin, or a polyester carbonate resin.

[0233] <I-2. Ratio of structural units>

[0234] The thermoplastic resin may contain only one of the diol structural unit (bisphenol structural unit) (B), fluorene structural unit (F) and binaphthyl structural unit (N) derived from a specified compound such as phenols, or may contain two or more thereof. The ratio of the diol structural unit (B), fluorene structural unit (F) and binaphthyl structural unit (N) is not particularly limited and may be any value. For example, the content of the specified diol structural unit (B), fluorene structural unit (F) and binaphthyl structural unit (N) based on the total molar number may be, for example, 10 to 100 mol%, 30 to 70 mol%, 40 to 60 mol% or 45 to 55 mol%.

[0235] In addition, the fluorene structural unit (F) and the binaphthyl structural unit (N) may be used in combination in the thermoplastic resin. In this case, the molar ratio of the fluorene structural unit (F) to the binaphthyl structural unit (N) is preferably 30:70 to 90:10, more preferably 40:60 to 80:20, and further preferably 50:50 to 70:30.

[0236] In the thermoplastic resin, the silane structural unit (S) is bonded to the terminal of the structural unit (A), for example, a predetermined diol structural unit (B), a fluorene structural unit (F) or a binaphthyl structural unit (N), and the silane structural unit (S) is contained only in a molar number substantially equal to the total molar number of the predetermined diol structural unit (B), the fluorene structural unit (F) and the binaphthyl structural unit (N) for the following reasons. In the polymerization reaction of the above-mentioned silane compound with the hydroxyl group of the diol compound, the alkoxy group or the monoaryloxy group in the silane compound is separated to form the silane structural unit (S). Therefore, generally, in the thermoplastic resin, the molar number of the silane structural unit (S) is equal to the total molar number of the fluorene structural unit (F) and the binaphthyl structural unit (N).

[0237] When the silane structural unit (S) is arranged at both ends of the above-mentioned structural unit (B), (F) or (N) derived from the diol, the molar number of the silane structural unit (S) is sometimes slightly excessive compared to the total molar number of the structural units (B), (F) and (N). For example, the molar number of the silane structural unit (S) can be about 1.01 times the total molar number of the structural units (B), (F) and (N).

[0238] Thus, the molar number of the silane structural unit (S) in the thermoplastic resin is, for example, 1.00 to 1.05 times, preferably 1.00 to 1.03 times, and more preferably 1.00 to 1.01 times the total molar number of the structural units (B) and (F) derived from the diol and the binaphthyl structural unit (N).

[0239] In the thermoplastic resin, the proportion of the arbitrary structural unit (Z) in all the structural units is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, particularly preferably 5 mol% or less, and the arbitrary structural unit (Z) may not be contained.

[0240] In addition, in the thermoplastic resin, the total amount of the silane structural unit, the diol structural unit (B), (F) and (N) in the total structural units is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more. In addition, the thermoplastic resin may be composed only of the silane structural unit and the prescribed diol structural unit (B), fluorene structural unit (F) or binaphthyl structural unit (N).

[0241] <I-3. Properties of thermoplastic resins>

[0242] The weight average molecular weight of the thermoplastic resin is, for example, 5,000 to 100,000, preferably 5,000 to 50,000, 5,000 to 60,000, or 6,000 to 45,000, more preferably 6,000 to 30,000, 7,000 to 40,000, 8,000 to 45,000, or 8,000 to 38,000. The weight average molecular weight of the thermoplastic resin is further preferably 9,000 to 36,000, 10,000 to 32,000, or 10,000 to 25,000, more preferably 12,000 to 22,000, particularly preferably 15,000 to 20,000.

[0243] The glass transition temperature (Tg) of the thermoplastic resin according to JIS K 7121 is preferably 105 to 170° C., preferably 110 to 165° C. The range of Tg of the thermoplastic resin is preferably 112 to 163° C., more preferably 120 to 155° C., and further preferably 125 to 152° C.

[0244] In the thermoplastic resin, the refractive index (nd) is preferably 1.600 to 1.750, more preferably 1.630 to 1.730, further preferably 1.650 to 1.725, and particularly preferably 1.660 to 1.720 or 1.665 to 1.715. Generally, the refractive index (nd) of the thermoplastic resin that can be used for optical applications is preferably higher, so the lower limit is important. In one embodiment of the present invention, the thermoplastic resin is preferably Figure 1 As exemplified above, the refractive index (nd) has a value of 1.670 or more. The refractive index (nd) of the thermoplastic resin is preferably 1.675 or more, more preferably 1.680 or more, and even more preferably 1.685 or more.

[0245] The upper limit of the refractive index (nd) of the thermoplastic resin is not particularly critical, but the thermoplastic resin in one embodiment of the present invention has a refractive index (nd) of 1.720 or less.

[0246] In thermoplastic resins, the Abbe number (ν) of the thermoplastic resin is preferably 15.0 to 27.0, more preferably 15.0 to 25.0, 15.0 to 23.0 or 15.0 to 22.0, and further preferably 15.0 to 21.0 or 15.5 to 20.5. In thermoplastic resins, especially thermoplastic resins that can be used for optical applications, it is preferred to have a high refractive index, and in thermoplastic resins with a high refractive index, the value of the Abbe number (ν) generally tends to decrease.

[0247] However, it can be said that optical thermoplastic resins having a high Abbe number (ν) are also useful. In one embodiment of the present invention, the thermoplastic resin is Figure 1 As exemplified, it has an Abbe number (ν) of 15.0 or more. The Abbe number (ν) of the thermoplastic resin is preferably 16.0 or more, more preferably 16.5 or more or 17.0 or more, further preferably 17.5 or more, and particularly preferably 18.0 or more.

[0248] For example, in thermoplastic resins used for optical applications, it is sometimes desired that the thermoplastic resin has a high refractive index as described above and a relatively large Abbe number (ν). As described above, the thermoplastic resin in one embodiment of the present invention has a relatively large value not only in terms of refractive index but also in terms of Abbe number.

[0249] Specifically, the values ​​of the refractive index (nd) and the Abbe number (νd) of the thermoplastic resin of the present invention preferably satisfy the relationship of the following formula (I).

[0250] Refractive index (nd) > -0.0078 × Abbe number (νd) + 1.8293… (I)

[0251] In particular, it is preferred that the thermoplastic resin satisfy the relational expression (I) when the refractive index (nd) is in the range of 1.640 to 1.730 and the Abbe number (νd) is in the range of 15.0 to 24.0.

[0252] In addition, it is preferred that the relationship (I) is satisfied in a thermoplastic resin not including a carbonate bond, for example, a thermoplastic resin in which aliphatic hydroxyl groups of a silane compound and a dihydroxy compound are bonded via a silyl ether bond.

[0253] like Figure 1 As shown, in the thermoplastic resins of Examples 1 to 5, the relationship of the above formula (I) is satisfied, and high refractive index and Abbe number are achieved.

[0254] Furthermore, it is more preferable that the values ​​of the refractive index (nd) and the Abbe number (νd) of the thermoplastic resin satisfy the relationship of the following formula (I-1) or (I-2).

[0255] -0.0080×Abbe number (νd)+1.861>Refractive index (nd)>-0.0078×Abbe number (νd)+1.8293…(I-1)

[0256] -0.0080×Abbe number (νd)+1.852>Refractive index (nd)>-0.0078×Abbe number (νd)+1.8293…(I-2)

[0257] For example, according to Figure 1 As can be seen, in the thermoplastic resins of Examples 1 to 5, the relationship of y(refractive index (nd))=0.0091×X(Abbe number (νd))+1.8638 is substantially established, and the thermoplastic resins of Examples 1 to 5 satisfy the relationship of the above-mentioned formulas (I-1) and (I-2).

[0258] The relationship between formulae (I-1) and (I-2) is similar to formula (I), and is particularly preferably satisfied in a thermoplastic resin having a refractive index (nd) value of 1.640 to 1.730 and an Abbe number (νd) within a range of 15.0 to 24.0.

[0259] In the thermoplastic resin, the YI value measured in accordance with JIS K 7105 is preferably 15.0 or less. The YI value of the thermoplastic resin is more preferably 12.0 or less, further preferably 10.0 or less, and particularly preferably 8.0 or less.

[0260] In the thermoplastic resin, the ratio of the total weight of silicon atoms (total Si amount) based on the total weight of the thermoplastic resin is, for example, 0.4 to 10.0 mass %, preferably 1.0 to 10.0 mass %, more preferably 1.2 to 8.0 mass %, further preferably 1.5 to 7.0 mass %, particularly preferably 2.0 to 6.5 mass %, for example 2.0 to 4.0 mass %.

[0261] In the polymer chain of the thermoplastic resin, the ratio of the Ph terminal groups derived from carbonate, i.e., -OC(O)O-Ph terminal groups, is preferably 0.1 to 20 μeq / g, more preferably 0.5 to 18 μeq / g, further preferably 1.0 to 16 μeq / g, and particularly preferably 1.5 to 12 μeq / g.

[0262] The ratio of the Ph terminal groups derived from carbonate is preferably 1 to 20 mol %, more preferably 2 to 18 mol %, further preferably 3 to 15 mol %, particularly preferably 4 to 12 mol %, based on the number of all terminal groups in the polymer chain of the thermoplastic resin.

[0263] In the polymer chain of thermoplastic resin, the Ph terminal group from silyl ether, i.e., OSiRs 1 Rs 2 - The terminal group of OPh (Rs 1 and Rs. 2 The ratio of (as otherwise defined) is preferably 5 to 200 μeq / g, more preferably 10 to 150 μeq / g, further preferably 15 to 120 μeq / g, and particularly preferably 20 to 100 μeq / g.

[0264] The ratio of Ph terminal groups derived from silyl ether is preferably 30 to 99 mol %, more preferably 40 to 95 mol %, further preferably 50 to 90 mol %, particularly preferably 60 to 85 mol %, based on the number of all terminal groups in the polymer chain of the thermoplastic resin.

[0265] In addition, in the polymer chain of the thermoplastic resin, an alkoxy terminal group such as an OMe terminal group derived from a silyl ether, such as -OSiRs 1 Rs 2 -OMe terminal group (Rs 1 and Rs. 2 The ratio of (as otherwise defined) is preferably 5 to 300 μeq / g, more preferably 20 to 250 μeq / g, further preferably 40 to 200 μeq / g, and particularly preferably 60 to 200 μeq / g.

[0266] The ratio of the alkoxy terminal groups such as Me terminal groups derived from silyl ether is preferably 10 to 99 mol %, more preferably 20 to 90 mol %, further preferably 30 to 80 mol %, particularly preferably 40 to 70 mol %, based on the number of all terminal groups in the polymer chain of the thermoplastic resin.

[0267] Thermoplastic resin polymers may contain impurities to some extent. For example, in the thermoplastic resin polymer, the content of impurities derived from raw materials such as formic acid and impurities such as organic phosphorus compounds may be, for example, 5 ppm to 100 ppm by weight, 10 ppm to 70 ppm by weight, or 20 ppm to 50 ppm by weight, based on the total weight.

[0268] In addition, a small amount of catalyst used in the polymerization reaction for production may remain in the thermoplastic resin. For example, the residual catalyst may be contained in an amount of about 5 μmol to 100 μmol, 15 μmol to 80 μmol, 25 μmol to 60 μmol, or 30 μmol to 50 μmol relative to 1 mol of all dihydroxy compounds used in the production of the polymer of the thermoplastic resin in terms of metal conversion.

[0269] [II. Composition (thermoplastic resin composition)]

[0270] The thermoplastic resin composition of the present invention preferably contains the thermoplastic resin which is the above-mentioned polysilicone resin as a main component. The thermoplastic resin composition of the present invention may contain the following components in addition to the thermoplastic resin.

[0271] <II-1. Low molecular weight compounds (cyclic compounds)>

[0272] The thermoplastic resin composition may contain a compound or oligomer having a weight average molecular weight of 1000 or less. For example, a low molecular weight cyclic compound represented by the following general formula (T) may be contained. The cyclic compound represented by the following general formula (T) is considered to be mainly derived from the above-mentioned component B.

[0273]

[0274] (In the general formula (T),

[0275] R 1 and R 2 Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

[0276] In R 1 and R 2 In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 14 or 1 to 10, the total number of carbon atoms is more preferably 1 to 6, and the total number of carbon atoms is particularly preferably 1 or 2.

[0277] In addition, in R 1 and R 2 In the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, the total number of carbon atoms is more preferably 6 to 12, and the total number of carbon atoms is particularly preferably 6 to 8.

[0278] As R 1 and R 2 Preferred specific examples include methyl, ethyl, propyl, phenyl, benzyl and the like, and methyl, phenyl and the like are more preferred.

[0279] In the general formula (T), Ra and Rb are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and containing one or more heteroatoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R h .

[0280] Ra and Rb are preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N and S and may have a substituent. They are more preferably a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may have a substituent, and further preferably a hydrogen atom or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0281] In the general formula (T), X represents a single bond or a fluorenyl group which may have a substituent. X is preferably a single bond or a fluorenyl group which may have a substituent and has a total carbon number of 12 to 20.

[0282] In the general formula (T), A and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms.

[0283] In the general formula (T), m and n are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.

[0284] In the general formula (T), a and b are each independently an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0285] Examples of substituents in the general formula (T) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidyloxy, mercapto, etc. In the general formula (T), when a substituent is included, the above range of carbon atoms is the total number of carbon atoms including the carbon atoms of the substituent.

[0286] Specific examples of the low molecular weight compound represented by the general formula (T) include compounds represented by the following formulae (T-1) to (T-4).

[0287]

[0288] The above-mentioned low molecular weight cyclic substance that can be included in the thermoplastic resin composition of the present invention is a substance that can be produced as a by-product due to the polymerization reaction used to manufacture the polyether resin. Due to the low molecular weight, the fluidity of the composition can be improved, and the moldability of the thermoplastic resin can be improved. In addition, the above-mentioned cyclic substance is a low molecular weight substance with a molecular structure close to that of the plasticizer. Therefore, in the thermoplastic resin containing the above-mentioned cyclic substance, even if the plasticizer is not added, the compatibility with other resins is high, and it is believed that the problem caused by the seepage of the plasticizer that does not need to be added can be reliably prevented. In addition, it is believed that the above-mentioned cyclic substance mainly comes from the above-mentioned B component. In the thermoplastic resin manufactured using only the A component, the above-mentioned cyclic substance is not contained, and it is believed that the effect of improving the moldability, etc. cannot be obtained.

[0289] In order to improve moldability, it is considered that a component with high plasticity may be contained in an appropriate amount, but if it is too much, there is a possibility that the mold may be contaminated during processing of the thermoplastic resin composition.

[0290] Based on the above, in the thermoplastic resin composition, the total content of the cyclic compound represented by the above formula (T) is preferably 15% by weight or less or 13% by weight or less, more preferably 10% by weight or less or 8.0% by weight or less, and further preferably 6.0% by weight or less or 4.0% by weight or less, based on the total weight of the thermoplastic resin composition. In addition, the total content of the cyclic compound represented by the above formula (T) contained in the thermoplastic resin composition is preferably 0.1% by weight or more and 15% by weight or less, more preferably 2.0% by weight or more and 13% by weight or less, further preferably 3.0% by weight or more and 11% by weight or less, and particularly preferably 4.0% by weight or more or more than 4.0% by weight (higher than 4.0% by weight) and 11% by weight or less, based on the total weight of the thermoplastic resin composition.

[0291] When the content of these cyclic substances is within the above range, it can be said that there is no problem with the properties of the thermoplastic resin composition, especially when it is used for optical applications. However, the thermoplastic resin composition does not need to contain the above cyclic substances.

[0292] <II-2. Resins other than polyether resins>

[0293] The thermoplastic resin composition may contain a thermoplastic resin that is not equivalent to the above-mentioned polyether resin, such as a polycarbonate resin. Regarding the type of polycarbonate resin, there is no particular limitation as long as it is a resin containing a -[O-R-OCO]- unit having a carbonate bond in the main chain of the molecule (R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure). In addition, in the thermoplastic resin composition, the polycarbonate resin may include a polyester carbonate resin and a polyester resin. Moreover, the polyester carbonate resin and the polyester resin are also the same, as long as they are a resin containing a -[O-R-OC]- unit having a carbonate bond in the main chain of the molecule (R is as described above), there is no particular limitation.

[0294] The weight average molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and further preferably 15,000 to 60,000.

[0295] The thermoplastic resin composition may include resins other than polyether resins, preferably thermoplastic resins. There is no particular limitation on the type of thermoplastic resin as a secondary component. In addition to polycarbonate resins and polyester carbonate resins, acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyether sulfone, cellophane, aromatic polyamide, etc. may also be cited.

[0296] In the composition, the ratio of the total weight of silicon atoms (total Si amount) based on the total weight of the composition is preferably 0.1 to 20 mass %, more preferably 0.2 to 15 mass %, particularly preferably 0.3 to 10 mass %.

[0297] The use of a thermoplastic resin with a high Si content enables the production of an excellent characteristic composition. By mixing a thermoplastic resin having a Si content of, for example, 0.1% by mass or more with a resin substantially free of silyl ether structural units, preferably a polycarbonate resin, the resulting composition can have both excellent impact resistance and fluidity.

[0298] In addition, in the composition comprising thermoplastic resin, phenolic compounds, unreacted and residual silane compounds, carbonate compounds and diol compounds that can be generated as by-products of polymerization reactions can be included. Phenolic compounds and diphenyl carbonate as impurities can also become the reasons for the strength reduction and odor generation when forming a molded body, so it is preferred that their content is as little as possible. Therefore, the content of phenolic compounds, silane compounds, carbonate compounds and diol compounds can be reduced to a level that cannot be detected, and from the viewpoint of productivity, they can be contained in the composition in a range that does not damage the effect. In addition, based on the gross weight of the composition, by containing a predetermined amount of monomer residues, for example 1 to 1000 ppm by weight, preferably 10 to 900 ppm, more preferably 20 to 800 ppm of monomers, the effect of improving the fluidity during molding can be obtained, and plasticity can be made good when the resin is melted. In the composition of the present invention, an aromatic monohydroxy compound represented by an aromatic alcohol such as phenol may be contained in an amount of, for example, more than 300 mass ppm or more, more than 500 mass ppm or more, or more than 700 mass ppm or more.

[0299] <II-3. Additives>

[0300] The thermoplastic resin composition may contain an additive. Examples of the additive include antioxidants. As the antioxidant, a phosphite antioxidant is preferred. In addition, the thermoplastic resin composition preferably contains an antioxidant used in the polymerization reaction for producing the polyether resin.

[0301] The addition ratio of the antioxidant in the thermoplastic resin composition is preferably 0.001 parts by mass or more (about 10 parts by mass or more), more preferably 0.01 parts by mass or more (about 100 parts by mass or more), and further preferably 0.1 parts by mass or more (about 1000 parts by mass or more), relative to 100 parts by mass of the total weight of the composition. In addition, the addition ratio of the antioxidant in the thermoplastic resin composition is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, further preferably 0.7 parts by mass or less (about 7,000 parts by mass or less), and particularly preferably 0.5 parts by mass or less (about 5,000 parts by mass or less), relative to 100 parts by mass of the total weight of the composition.

[0302] The thermoplastic resin composition may contain only one antioxidant or two or more antioxidants. When two or more antioxidants are contained, the total amount thereof is preferably within the above range.

[0303] The thermoplastic resin composition of the present invention may contain the following additives as minor components.

[0304] Inactivation Agents

[0305] In the thermoplastic resin of the present invention, after the polymerization reaction is completed, in order to maintain thermal stability, the catalyst can be removed or deactivated. The method of deactivating the catalyst by adding a known acidic substance can be appropriately implemented. As the acidic substance, specifically, the following can be appropriately used: esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; triphenyl phosphate, diphenyl phosphate Phosphates such as phosphates, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonates 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 stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfuric acids such as dimethylsulfuric acid; organic halides such as benzyl chloride, etc.

[0306] As a deactivator for deactivating the catalyst, alkyl phosphate metal salts such as distearate zinc phosphate and monostearyl zinc phosphate may be used.

[0307] The above-mentioned deactivator can be used in an amount of, for example, 0.001 to 50 times the amount of the catalyst, and preferably 0.01 to 30 times the amount of the catalyst.

[0308] A stabilizer may be added to the thermoplastic resin of the present invention. As stabilizers, heat stabilizers and the above-mentioned antioxidants may be exemplified. When the stabilizer is added, the addition ratio of the stabilizer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.02 parts by mass or more relative to 100 parts by mass of the thermoplastic resin, and preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and further preferably 1.0 parts by mass or less. The stabilizer may contain only one type in the thermoplastic resin composition, or may contain two or more types. When containing two or more types, it is preferred that their total amount is within the above range.

[0309] As heat stabilizers, phenolic, phosphorus, and sulfur-based heat stabilizers can be cited. Specifically, phosphorus-containing oxygen acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonate compounds can be cited. In addition, at least one selected from the group consisting of phosphite compounds (a) in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group of 1 to 25 carbon atoms, phosphorous acid (b), and tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-diphosphonate (c) can be cited. Specific examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl) phosphite, tris(mononyl / dinonylphenyl) phosphite, trinonylphenyl phosphite, tris(octylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, bis(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol 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, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, etc. These may be used alone or in combination of two or more.

[0310] Examples of the organic phosphite compound include "ADK STAB 1178" (trade name, hereinafter the same), "ADK STAB 2112", and "ADK STAB HP-10" manufactured by ADEKA, "JP-351", "JP-360", and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "Irgafos 168" manufactured by BASF.

[0311] Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tri(nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate.

[0312] When a heat stabilizer is added, the addition ratio of the heat stabilizer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.03 parts by mass or more, and is preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, and further preferably 0.5 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin.

[0313] The thermoplastic resin composition may contain only one type of the heat stabilizer or two or more types thereof. When two or more types are contained, it is preferred that the total amount thereof is within the above range.

[0314] Flame retardants

[0315] The thermoplastic resin of the present invention may be compounded with various additives within the scope of the present invention. As a flame retardant, an organic metal salt flame retardant, a phosphorus flame retardant, a silicone flame retardant, etc. may be compounded. As a flame retardant that can be used in the present invention, the flame retardant (flame retardant composition) described in paragraphs 0085 to 0093 of Japanese Patent Publication No. 2016-183422 can be exemplified, and these contents are cited in this specification.

[0316] UV absorber

[0317] As the ultraviolet absorber, in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxalylanilide compounds, malonic acid ester compounds, hindered amine compounds, and salicylic acid phenyl ester compounds can also be listed. Among these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred. In particular, as specific examples of benzotriazole compounds, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[2′-hydroxy-3′, 5′-bis(α, α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2′-hydroxy-3′, 5′-di-tert-butyl-phenyl)-benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′, 5′-di-tert-butyl-phenyl )-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amyl)-benzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine-2-yl]-5-(octyloxy)phenol, 2,2′-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl)-methylene]-malonic 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 2-(tert-butyl)phenol, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], [methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate, etc. Among the above, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] are preferred.In addition, as specific examples of benzophenone-based ultraviolet absorbers, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2',4,4'-tetrahydroxy-benzophenone, etc. can be listed. In addition, as specific examples of phenyl salicylate-based ultraviolet absorbers, phenyl salicylate, 4-tert-butyl-phenyl salicylate, etc. can be listed. Specific examples of triazine-based ultraviolet absorbers include 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-(octyloxy)phenol, etc. Specific examples of hindered amine-based ultraviolet absorbers include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, etc.

[0318] When a UV absorber is added, the addition ratio of the UV absorber is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 3 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the thermoplastic resin.

[0319] The ultraviolet absorber may be used alone or in combination of two or more. When two or more ultraviolet absorbers are used, the total amount is preferably within the above range.

[0320] Release agent

[0321] As the release agent, there can be listed the release agents such as carboxylic acid esters, polysiloxane compounds, paraffin (polyolefin system). Specifically, there can be listed at least one compound selected from 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 silicone oils. As aliphatic carboxylic acids, saturated or unsaturated aliphatic monocarboxylic acids, dicarboxylic acids or tricarboxylic acids can be listed. Among them, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monocarboxylic acids or dicarboxylic acids with 6 to 36 carbon atoms, and more preferably aliphatic saturated monocarboxylic acids with 6 to 36 carbon atoms. As specific examples of aliphatic carboxylic acids, there can be listed palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, beeswax acid, tritriacontanoic acid, montanic acid, glutaric acid, adipic acid, azelaic acid, etc. As the aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol, the same carboxylic acids as the above-mentioned aliphatic carboxylic acids can be used. On the other hand, as alcohol, saturated or unsaturated monohydric or polyhydric alcohols can be listed. These alcohols may have substituents such as fluorine atoms and aromatic groups. Among these, monohydric or polyhydric saturated alcohols with a carbon number of 30 or less are preferred, and aliphatic saturated monohydric or polyhydric alcohols with a carbon number of 30 or less are more preferred. Among them, aliphatic also includes alicyclic compounds. As specific examples of alcohols, octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, ditrimethylolpropane, dipentaerythritol, etc. can be listed. In addition, the above-mentioned ester compound may contain aliphatic carboxylic acid and / or alcohol as impurities, or it may be a mixture of multiple compounds. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture with palmitic acid beeswax ester as the main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. As aliphatic hydrocarbons with a number average molecular weight of 200 to 15000, liquid paraffin, paraffin, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, α-olefin oligomers with 3 to 12 carbon atoms, etc. can be listed. Among them, aliphatic hydrocarbons also include alicyclic hydrocarbons. In addition, these hydrocarbon compounds can also be partially oxidized. Among these, paraffin wax, polyethylene wax or partial oxides of 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 either single substances or mixtures of aliphatic hydrocarbons having different constituent components or molecular weights, as long as the main component is within the above range. Examples of polysiloxane 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.

[0322] When a release agent is added, the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and is preferably 2 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the thermoplastic resin.

[0323] The release agent may be used alone or in combination of two or more. When two or more release agents are used, the total amount is preferably within the above range.

[0324] Colorants

[0325] The colorant may be any of a dye and a pigment, and examples thereof include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as Prussian blue. In addition, as organic pigments and organic dyes used as colorants, for example, phthalocyanine dyes (dye or pigment is referred to as dye pigment, the same below) such as copper phthalocyanine blue and copper phthalocyanine green can be listed; azo dyes such as nickel azo yellow; condensed polycyclic dyes such as thioindigo, pyrenone, perylene, quinacridone, dioxazine, isoindolinone, quinophthalone; quinoline, anthraquinone, heterocyclic, methyl dyes, etc. Among these, titanium oxide, carbon black, cyanine, quinoline, anthraquinone, phthalocyanine dyes, etc. are preferred from the viewpoint of thermal stability.

[0326] In order to improve the workability during extrusion and the dispersibility in the resin composition, the colorant may be used in the form of a masterbatch with a polystyrene resin, a polycarbonate resin or an acrylic resin.

[0327] When the colorant is matched, the addition ratio of the colorant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 2 parts by mass or less, and 0.1 parts by mass or more relative to 100 parts by mass of the thermoplastic resin. The colorant can be used only one kind, or two or more kinds. When two or more kinds are used, the total amount is preferably within the above range.

[0328] [III. Molded body]

[0329] Next, the molded article according to the present invention comprising the thermoplastic resin or the thermoplastic resin composition of the present invention will be described.

[0330] The molded article of the present invention comprises the above-mentioned thermoplastic resin or thermoplastic resin composition. The molded article is obtained by molding these thermoplastic resins or thermoplastic resin compositions. There is no particular limitation on the molding method of the molded article, and examples of the molded article include injection molded articles, compression molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, compressed air molded articles, and the like.

[0331] The molded article of the present invention is, for example, an optical lens, an optical film, etc. The thermoplastic resin of the present invention is suitable for optical applications, and the optical lens and optical film have particularly excellent properties. In addition, the optical lens that can include the molded article of the present invention has a refractive index, Abbe number, etc. in an appropriate range.

[0332] [IV. Method for producing thermoplastic resin]

[0333] <IV-1. Overview of production method>

[0334] The method for producing a thermoplastic resin includes at least a step of polymerizing the above-mentioned silane compound and diol compound as a linking agent. The silane compound functions as a supply source of silane bonding sites, and the A component and the B component function as supply sources of their respective corresponding structural units.

[0335] The above-mentioned polymerization reaction can be schematically represented as follows. For example, when dimethyldiphenoxysilane is used as the silane compound, it reacts with the terminal hydroxyl group of the diol compound to form the main chain of the thermoplastic resin, and phenol (PhOH) is generated as a by-product. Therefore, in the polymerization step, it is preferred to carry out the polymerization reaction while removing the alcohol as a by-product, such as aromatic alcohol such as phenol, under reduced pressure while the mixture of the above-mentioned components is melted.

[0336] <IV-2. Ratio of monomers>

[0337] In the polymerization process for producing the thermoplastic resin, the ratio of the silane compound and the diol compound as monomers can be appropriately adjusted to achieve the above-mentioned preferred ratio of the structural units. For example, as described above, the ratio of the diol structural unit (B), the fluorene structural unit (F) and the binaphthyl structural unit (N) is not particularly limited, and the molar ratio of the monomer compounds equal to the target ratio of the structural units can be adopted.

[0338] For example, the contents of the diol compound (B') for forming the prescribed diol structural unit (B), the fluorene compound (F') for forming the fluorene structural unit (F), and the binaphthyl compound (N') for forming the binaphthyl structural unit (N) in the total diol compounds are, for example, 10 to 100 mol%, 30 to 70 mol%, 40 to 60 mol% or 45 to 55 mol%, respectively, based on the total molar number.

[0339] In addition, in the thermoplastic resin, a fluorene structural unit (F) and a binaphthyl structural unit (N) can be used in combination. In this case, the molar ratio of the fluorene compound (F') used to form the fluorene structural unit (F) and the binaphthyl compound (N') used to form the binaphthyl structural unit (N) is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and further preferably 40:60 to 60:40.

[0340] In addition, the silane structural unit (S) is bonded to the terminal of the diol structural unit (B), the fluorene structural unit (F) or the binaphthyl structural unit (N), and is contained only in a molar number substantially equal to the total molar number of the diol of the diol structural unit (B), the fluorene structural unit (F) and the binaphthyl structural unit (N). However, in the polymerization step, it is preferred to use the silane compound in a slightly excessive amount. For example, the molar number of the polymerized silane compound is 1.0 to 1.2 times, preferably 1.01 to 1.1 times, and more preferably about 1.02 to 1.06 times the total molar number of the A component and the B component. As described above, in the polymerization step, the amount (number of moles) of the silane compound is slightly excessive relative to the total amount (number of moles) of the diol compounds used to form the diol structural units (A). The excess silane compound is not used in the polymerization reaction and is removed from the reaction system. On the other hand, it is possible to prevent the silane structural units (S) from being insufficient in the thermoplastic resin obtained after the polymerization, and it is possible to reliably adjust the silane structural units (S) to be equal to the total number of moles of the diol structural units (A).

[0341] <II-3. Any monomer>

[0342] In the polymerization step for producing the thermoplastic resin, monomers other than the silane compound, component A and component B may be used. For example, monomers for forming the above-mentioned arbitrary structural unit (Z) may be used.

[0343] <II-4. Catalyst>

[0344] In the polymerization step, a catalyst may not be used, but for example, the following polymerization catalysts are preferably used.

[0345] First, as preferred specific examples of the polymerization catalyst, there can be listed metal acetates such as zinc acetate, lead acetate, manganese acetate, cobalt acetate, aluminum acetate, calcium acetate, potassium acetate, lithium acetate, magnesium acetate, sodium acetate, tin acetate, zirconium acetate, zirconium acetylacetonate (Zr(acac)), and other metal salts. Among these metal salts, as more preferred specific examples of the polymerization catalyst, there can be listed zinc acetate, lead acetate, manganese acetate, cobalt acetate, and the like.

[0346] As the polymerization catalyst, a phosphonium salt can be used, preferably a quaternary phosphonium salt. Specific examples of the phosphonium salt as the polymerization catalyst include alkyl phosphonium salts such as tetra-n-butylphosphonium bromide and tetra-n-butylphosphonium chloride; aryl phosphonium salts such as tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and phenoxytetraphenylphosphonium (TPPP); and alkylaryl phosphonium salts.

[0347] In addition, as the polymerization catalyst, a catalyst containing a basic compound can also be used. As the basic compound catalyst, alkali metal compounds, alkaline earth metal compounds, etc., for example, inorganic salts such as organic acid salts, carbonates, etc. of alkali metal and alkaline earth metal compounds, oxides, hydroxides, hydrides or alcoholates, etc. can be listed. Alternatively, as the basic compound catalyst, quaternary ammonium hydroxides and their salts, amines, phosphazenes, etc. can be used. In addition, these compounds can be used alone or in combination.

[0348] Among the above-mentioned basic compound catalysts, alkali metal carbonates or alkali metal hydroxides are more preferably included. As specific examples of more preferred catalysts, metal carbonates such as cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, etc.; catalysts of metal hydroxides such as cesium hydroxide, potassium hydroxide, sodium hydroxide, etc. can be listed.

[0349] Preferred specific examples of the amine-based catalyst include diazabicycloundecene (DBU: registered trademark) and the like, and preferred specific examples of the phosphazene-based catalyst include BTPP (tert-butylimidotripyrrolidinephosphine) and the like.

[0350] In addition, as a catalyst, a phosphonium salt can be used, preferably a quaternary phosphonium salt. Specific examples of the phosphonium salt as a polymerization catalyst include alkyl phosphonium salts such as tetra-n-butylphosphonium bromide and tetra-n-butylphosphonium chloride; aryl phosphonium salts such as tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and phenoxytetraphenylphosphonium salt (TPPP); alkylaryl phosphonium salts, etc.

[0351] As further specific examples of the catalyst in the polymerization reaction, the following catalysts can be mentioned.

[0352] Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborate, potassium phenylborate, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, and dicesium phenyl phosphate; alcoholates and phenolates of sodium, potassium, lithium, and cesium; and disodium, dipotassium, dilithium, and dicesium salts of bisphenol A.

[0353] In addition, examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, and the like.

[0354] In addition, specific examples of basic boron compounds that can be used as catalysts in the polymerization process include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, strontium salts, and the like of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

[0355] Examples of the basic phosphorus compound that can be used as a catalyst in the polymerization step include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0356] Examples of the basic ammonium compound that can be used as a catalyst in the polymerization step include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0357] Examples of the amine compound that can be used as a catalyst in the polymerization step include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0358] In addition, as a polymerization catalyst, a polymerization catalyst known per se can be used, for example, preferably an antimony compound, a titanium compound, a germanium compound, a tin compound or an aluminum compound. As such a compound, for example, oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates, etc. of antimony, titanium, germanium, tin, and aluminum can be cited. In addition, these compounds can be used in combination of two or more. Among them, from the viewpoint of the melt stability and hue of the thermoplastic resin, preferably tin, titanium, and germanium compounds.

[0359] As the catalyst in the polymerization reaction, as mentioned above, it is possible to adopt a catalyst known per se, for example, compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium or lead elements etc. can be used. Specifically, oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates etc. containing these elements can be listed. Among them, from the viewpoint of the melt stability, hue and phase of the thermoplastic resin, and the few insoluble foreign matter in the polymer, compounds of oxides, acetates, alcoholates etc. of manganese, magnesium, zinc, titanium and cobalt are preferred. Manganese, magnesium and titanium compounds are more preferred. These compounds can be used in combination of two or more.

[0360] As the catalyst in the polymerization reaction, it is preferred to use salts of zinc, tin, zirconium, and lead, which can be used alone or in combination. In addition, they can also be used in combination with the above-mentioned alkali metal compounds and / or alkaline earth metal compounds.

[0361] As the catalyst in the polymerization reaction, specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxytin, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxyzirconium, lead (II) acetate, lead (IV) acetate, zirconium acetate, tetrabutoxytitanium, etc. can be used. Among them, zinc acetate, zirconium acetate and tetrabutoxytitanium are preferred, and tetrabutoxytitanium is more preferred.

[0362] The above-mentioned catalyst can be prepared by a known method, or a commercially available catalyst can be used.

[0363] In addition, in the thermoplastic resin and the thermoplastic resin composition described in detail below, it is preferred that a catalyst, for example, an alkali metal compound catalyst or an alkaline earth metal compound catalyst, is substantially completely removed in advance.

[0364] <II-5. Additives>

[0365] In the polymerization reaction for producing the thermoplastic resin, an additive may be used, and an antioxidant is preferably used. In the polymerization step, the order of mixing may be arbitrary, and it is preferred that the polymerization reaction is started after the silane compound, component A, and component B as monomer compounds are mixed and the antioxidant is pre-mixed in the monomer compound. In the polymerization reaction, the monomer compound is preferably polymerized in the presence of the above-mentioned catalyst.

[0366] Examples of the antioxidant include phosphite-based additives, phenol-based antioxidants, hindered phenol-based antioxidants, bisphenol-based antioxidants, polyphenol-based antioxidants, and sulfur-based antioxidants, and phosphite-based additives are preferably used.

[0367] As the phosphite antioxidant, specifically, organic phosphate compounds, organic phosphite compounds, organic phosphonate compounds, etc. can be cited. In addition, at least one selected from the group consisting of a phosphite compound (a) in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group having 1 to 25 carbon atoms, phosphorous acid (b), and tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-diphosphonate (c) can be cited. Specific examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl) phosphite, tris(mononyl / dinonylphenyl) phosphite, trinonylphenyl phosphite, tris(octylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, bis(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol 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, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, etc. These may be used alone or in combination of two or more.

[0368] Examples of the organic phosphite compound include "ADK STAB 1178 (trade name, hereinafter the same)", "ADK STAB 2112", and "ADK STAB HP-10" manufactured by ADEKA, "JP-351", "JP-360", and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "Irgafos 168" manufactured by BASF.

[0369] Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tri(nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate.

[0370] Examples of the phenolic antioxidant include 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′-butylenebis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]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 -Dimethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene Bis(oxyethylene)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-triazin-2-ylamino)phenol, etc.

[0371] Examples of the phenolic antioxidant include "IRGANOX 1010" (registered trademark, hereinafter the same) and "IRGANOX 1076" manufactured by BASF, and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by ADEKA.

[0372] When an antioxidant is added, the antioxidant is preferably added in an amount of 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.05 parts by mass or more, relative to 100 parts by mass of the total monomer compounds of the thermoplastic resin, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, further preferably 0.3 parts by mass or less or 0.1 parts by mass or less. In addition, the phosphorus content in the thermoplastic resin caused by the phosphite-based antioxidant or the like is also, for example, 1 part by mass or less, more preferably 0.5 parts by mass or less, and further preferably 0.1 parts by mass or less.

[0373] The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

[0374] By adding an antioxidant to a thermoplastic resin produced by a polymerization reaction, a thermoplastic resin composition containing an antioxidant can be produced. In addition, in the past, in order to prevent the thermal history of the additive itself generated during the polymerization reaction or to adjust the amount of addition according to the purpose of use, the additive was mostly added after the production of the resin.

[0375] However, according to the method for producing a thermoplastic resin of the present invention in which an antioxidant is added to a monomer compound before the polymerization reaction, the hue-improving effect in the produced thermoplastic resin is remarkable.

[0376] <II-6. Polymerization reaction conditions>

[0377] In the polyreaction that makes the above-mentioned monomer compound polymerization, the mixture of above-mentioned each component is melted, forms molten state, removes under reduced pressure as by-product the alcohol from carbonate compound, for example aryl alcohol, methyl alcohol etc. of phenol etc. By setting reaction conditions like this, polyreaction can be carried out efficiently.

[0378] In the polymerization step, the polymerization reaction is preferably performed under a pressure of 400 Pa or less. That is, the pressure during the polymerization reaction is preferably within a range of 400 Pa or less.

[0379] In the polymerization step, it is preferred to maintain a certain degree of time, a state of normal pressure without decompression, or a state of not significantly decompressing, and then reduce the pressure in the system to further perform the polymerization reaction. For example, in the polymerization step, it is preferred to gradually reduce the reaction pressure to 400Pa or 200Pa in a manner from the initial atmospheric pressure to 40,000Pa, 27,000Pa, 24,000Pa, 20,000Pa, 16,000Pa, 10,000Pa, 8,000Pa, 5,000Pa, 4,000Pa, 2,000Pa, 400Pa, 400Pa or less, or 200Pa or less. For example, in the polymerization step, the pressure can be reduced in stages from the initial atmospheric pressure to 40,000Pa, 20,000Pa, 10,000Pa, 5,000Pa, or 200Pa or less. In this way, the decompression step of reducing the pressure in the reaction system stepwise and increasing the degree of decompression midway is preferred because it is possible to efficiently remove alcohol as a by-product while suppressing distillation of the raw material.

[0380] The time of the polymerization step is appropriately determined based on the conditions such as the type of the target thermoplastic resin, pressure, temperature, etc. For example, the total time spent in the polymerization step is within 5 to 10 hours. More specifically, the reaction time before the decompression in the reaction system is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after the decompression is 1 to 5 hours, preferably 2 to 4 hours.

[0381] In the polymerization step, the polymerization reaction temperature is preferably in the range of 150 to 300° C. More preferably, the polymerization reaction temperature is 160 to 280° C., further preferably 170 to 270° C., and particularly preferably 180 to 260° C. In addition, the polymerization reaction temperature may preferably range from 190 to 290° C., 210 to 280° C., 230 to 270° C., 240 to 260° C., and the like.

[0382] In the polymerization step, the value of the ratio of the molar amount of the catalyst to the total molar amount of the monomer compounds (molar ratio: that is, molar amount of the catalyst / molar amount of the monomer compounds) is preferably 1.0×10 -7 ~1.0×10 -2 (mol / mol: 0.1~10000μmol / mol or 1.0×10 -4 The above molar ratio is more preferably 1.0×10 -7 ~2.0×10 -5 mol / mol (or 0.1~20μmol / mol).

[0383] Example

[0384] <Method for measuring refractive index (nd)>

[0385] Refractive index (nd):

[0386] The 3 mm thick rectangular sheets composed of polycarbonate copolymers produced in the examples and comparative examples described below were measured using an Abbe refractometer in accordance with the method of JIS-K-7142.

[0387] <Method for measuring Abbe number (νd)>

[0388] The refractive index of the 3 mm thick rectangular plates made of polycarbonate resin prepared in Examples and Comparative Examples at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. was measured using an Abbe refractometer, and the Abbe number was calculated using the following formula.

[0389] νd=(nd-1) / (nF-nC)

[0390] nd: refractive index at wavelength 589nm

[0391] nC: refractive index at a wavelength of 656nm

[0392] nF: refractive index at a wavelength of 486nm

[0393] <Measurement of glass transition temperature (Tg)>

[0394] A 5-12 mg test piece was used as a measurement sample. The test piece was weighed in 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 upper part of the sample container was sealed with an AI autosampler cap to prepare a measurement sample.

[0395] The Tg was measured using a differential scanning calorimeter (DSC) in a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard substance in the reference cell. The measurement sample adjusted to 30°C was heated to 280°C at 20°C / min, then cooled to 30°C at 20°C / min. Then, the temperature was raised to 280°C at 10°C / min and the measurement was performed.

[0396] Measuring device: Differential scanning calorimeter (DSC) (product name "DSC-7020", manufactured by Hitachi High-Technologies Corporation)

[0397] <Measurement of polystyrene equivalent weight average molecular weight (Mw)>

[0398] GPC (gel permeation chromatography) was used, chloroform was used as the developing solvent, and standard polystyrene (Shodex STANDARD, SM-105) with known molecular weight (molecular weight distribution = 1) was used to prepare a calibration curve. The elution time and molecular weight value of each peak were plotted based on the measured standard polystyrene, and the calibration curve was obtained by approximation using a cubic equation.

[0399] Then, based on the obtained calibration curve, the weight average molecular weight (Mw) was determined as a polystyrene conversion value according to the following formula.

[0400] [Calculation formula]

[0401] Mw=Σ(W i ×M i ) / Σ(W i )

[0402] (In the above formula, i represents the i-th cut-off point when the molecular weight M is cut off, W i represents the weight of the i-th item, M i represents the molecular weight of the ith one. In addition, the molecular weight M represents the molecular weight converted to polystyrene at the same elution time of the calibration curve. )

[0403] [Measurement conditions]

[0404] ·Device: Labsolutions manufactured by Shimadzu Corporation

[0405] Chromatographic columns: guard column (Shodex GPC K-G 4A) × 1, analytical column (Shodex GPC K-805L) × 2

[0406] Solvent: Chloroform (HPLC grade)

[0407] Injection volume: 10μL

[0408] Sample concentration: 2000ppm

[0409] Solvent flow rate: 1mL / min

[0410] ·Measurement temperature: 40℃

[0411] Detector: RI

[0412] <Measurement of the content ratio of low molecular weight compounds having a weight average molecular weight (Mw) of 1,000 or less>

[0413] The proportion of low molecular weight compounds having an Mw of 1,000 or less in the polycarbonate resin can be calculated based on data obtained by GPC analysis under the above conditions, for example, from the ratio of the area at retention time 20.5 min to 21.5 min / the area at retention time 0 min to 21.5 min (GPC area ratio).

[0414] That is, GPC analysis is performed under the conditions described in the column "Measurement of polystyrene-equivalent weight average molecular weight (Mw)". Based on the ratio of the GPC area (A) of the peak with a retention time (Retention Time) of 21.5 minutes or less, which is considered to correspond to the amount of all compounds contained in the sample of the polycarbonate resin, and the GPC area (B) of the peak confirmed between 20.5 minutes and 21.5 minutes, which is considered to correspond to the amount of low molecular weight compounds with a weight average molecular weight of 1,000 or less, the content ratio of the low molecular weight compounds is measured (B / A×100(%)), and the content ratio of the low molecular weight compounds can be calculated.

[0415] <Synthesis of di(1-naphthyl)dimethoxysilane (DNDMS)>

[0416] In a 500mL four-necked flask equipped with a magnetic stirrer, a thermometer, and a dropping funnel, magnesium (12.30g, 0.506mol) and iodine (3 grains) were placed, and the system was replaced with a nitrogen atmosphere. THF50mL was added to the flask, and a mixed solution of THF150mL, 1-bromonaphthalene (91.11g, 0.44mol), and tetramethoxysilane (30.44g, 0.2mol) was added to the dropping funnel, and stirring was started with a magnetic stirrer. Under a nitrogen stream, dripping from the dropping funnel was started, and the preparation of the Grignard reagent and the reaction with tetramethoxysilane were started. It took 50 minutes to drip the entire amount in the dropping funnel, and then heating with an oil bath was started, and heating reflux was performed for 3 hours. After the heating reflux was completed, air cooling and ice cooling were performed to reduce the temperature to 20°C. Keeping ice cooling, 40mL of methanol was added to stop the reaction. In another 1L flask, add a magnetic stirrer and 450mL of hexane, and stir with a magnetic stirrer. Inject the solution after the reaction is stopped into the stirring hexane, and the magnesium salt produced as a by-product in the reaction is precipitated as a white precipitate in almost all amounts. The magnesium salt is filtered and separated by vacuum filtration, and the filtered residue is washed twice with 100mL of toluene heated to 70°C and once with 100mL of hexane at room temperature. The solvent is distilled off from the filtrate after vacuum filtration using a rotary evaporator to obtain 86.35g of a crude product.

[0417] 40 g of toluene was added while the crude product was heated to 100°C, and after dissolution, it was filtered while hot under reduced pressure. The filtrate was stirred with a magnetic stirrer and a magnetic stirrer while air-cooling for 25 minutes and ice-cooling for 15 minutes to precipitate DNDMS. Finally, the white solid of DNDMS was filtered out with a Kiriyama funnel and washed twice with 50 mL of ice-cold hexane, thereby obtaining 55.13 g of a white solid containing DNDMS (yield 80%).

[0418] The obtained white solid was identified by NMR and GC. As a result, the NMR spectrum data was as follows, and the GC purity was 99.3%.

[0419] 1H NMR (500MHz, CDCl3): δ8.31 (dd, 2H), 8.05 (dd, 2H), 7.93 (d, 2H), 7.83 (dd, 2H), 7.49 (dd, 2H), 7.45-7.38 (m, 4H), 3.64 (s, 6H).

[0420] The molecular structure of the DNDMS thus obtained is shown in the following formula (1-2). In addition, the DNDMS synthesized in the above-mentioned synthesis example also contains isomers such as di(2-naphthyl)dimethoxysilane. In this way, even if the obtained DNDMS is a mixture of isomers shown in formula (1-3), it can be directly used in the subsequent polymerization reaction.

[0421]

[0422] <Synthesis of di(2-naphthyl)diethoxysilane (D2NDES)>

[0423] In a 500mL four-necked flask equipped with a magnetic stirrer, a thermometer, and a dropping funnel, magnesium (12.58g, 0.518mol) and iodine (1 grain) were placed, and the system was replaced with a nitrogen atmosphere. 50mL of THF was added to the flask, and a mixed solution of 150mL of THF, 2-bromonaphthalene (93.18g, 0.45mol), and tetraethoxysilane (41.67g, 0.2mol) was added to the dropping funnel, and stirring was started with a magnetic stirrer. Under a nitrogen stream, dripping from the dropping funnel was started, and the preparation of the Grignard reagent and the reaction with tetramethoxysilane were started. It took 50 minutes to drip the entire amount in the dropping funnel, and then heating with an oil bath was started, and heating reflux was performed for 3.5 hours. After the heating reflux was completed, air cooling and ice cooling were performed to reduce the temperature to 20°C. Keeping ice cooling, 50mL of ethanol was added to stop the reaction. In other 1L flask, add magnetic stirrer and hexane 400mL, stir with magnetic stirring apparatus.In the hexane being stirred, inject the solution after reaction stops, and the magnesium salt of by-product is separated out as off-white precipitation in the reaction.By decantation, magnesium salt is filtered and separated from reaction solution, and residue is cleaned 2 times with hexane 50mL, and filtered under reduced pressure.Utilize rotary evaporator to remove solvent distillation from the filtrate after filtered under reduced pressure, obtain crude product 84.48g.

[0424] The crude product was distilled under reduced pressure to obtain 36.56 g of purified D2NDES (bp 202°C / 130Pa) as a yellowish white solid. 32.62 g of the distilled D2NDES was further purified by recrystallization. 11.6 g of hexane was added to D2NDES and heated to 45°C while stirring with a magnetic stirrer to completely dissolve it. After cooling to room temperature while stirring, 2 mg of crude crystals of D2NDES were added, and as a result, crystals of D2NDES began to precipitate. After further stirring at room temperature for 90 minutes, stir under ice-cooling for 10 minutes. The precipitated white solid was filtered out with a Kiriyama funnel and washed once with 30 mL of ice-cold hexane, thereby obtaining 28.6 g of a white solid containing high-purity D2NDES (the yield was 43% when the amount used for recrystallization was added).

[0425] The obtained white solid was identified by NMR and GC. As a result, the NMR spectrum data were as follows, and the GC purity was 99.4%.

[0426] 1 H NMR (500 MHz, CDCl 3 ): δ8.24(s, 2H), 7.86-7.83(m, 6H), 7.74(dd, 2H), 7.53-7.46(m, 4H), 3.95(q, 4H), 1.31(t, 6H).

[0427] The molecular structure of the D2NDES thus obtained is shown in the following formula (1-4). In addition, the D2NDES synthesized in the above synthesis example also contains isomers such as di(1-naphthyl)diethoxysilane, but even a mixture of isomers can be used directly in the subsequent polymerization reaction.

[0428]

[0429] <Synthesis of di(1-naphthyl)diethoxysilane (DNDES)>

[0430] In a 300mL four-necked flask equipped with a magnetic stirrer, a thermometer, and a dropping funnel, magnesium (3.91g, 0.161mol) and iodine (1 grain) were placed, and the system was replaced with a nitrogen atmosphere. 15mL of THF was added to the flask, and a mixed solution of 35mL of THF, 1-bromonaphthalene (28.99g, 0.14mol), and tetraethoxysilane (10.42g, 0.05mol) was added to the dropping funnel, and stirring was started with a magnetic stirrer. Under a nitrogen stream, dripping from the dropping funnel was started, and the preparation of the Grignard reagent and the reaction with tetramethoxysilane were started. The entire amount in the dropping funnel was dripped over 60 minutes, and then heating with an oil bath was started, and heating reflux was performed for 3 hours. After the heating reflux was completed, air cooling and ice cooling were performed to reduce the temperature to 20°C. While keeping ice cooling, 20mL of ethanol was added to stop the reaction. In another 500mL flask, add magnetic stirrer and hexane 150mL, stir with magnetic stirrer.In the hexane being stirred, inject the solution after reaction stops, and the magnesium salt of by-product is separated out as white precipitate substantially in full amount in the reaction.Magnesium salt is filtered and separated by vacuum filtration, and the filter residue is cleaned 3 times with hexane 50mL.Utilize rotary evaporator to remove solvent distillation from the filtrate after vacuum filtration, obtain crude product 26.33g.

[0431] While heating the crude product to 66°C, 100 mL of hexane was added, and the insoluble components were filtered while hot under reduced pressure. The filtered residue was washed with 50 mL of hexane also heated to 66°C. Hexane was distilled off from the filtrate using a rotary evaporator to obtain 23.71 g of a white solid for recrystallization. While heating the obtained white solid to 66°C again, hexane was added. As a result, it was completely dissolved at the stage of adding 6.4 g of hexane. Then, while stirring with a magnetic stirrer and a magnetic stirrer, air-cool for 20 minutes and ice-cool for 15 minutes to precipitate DNDES. Finally, the white solid of DNDES was filtered out with a Kiriyama funnel and washed twice with 20 mL of ice-cold hexane, thereby obtaining 14.27 g of a white solid containing DNDES (yield 77%).

[0432] The obtained white solid was identified by NMR. As a result, the NMR spectrum data were as follows.

[0433] 1 H NMR (500 MHz, CDCl 3 ): δ8.32(d, 2H), 8.11(dd, 2H), 7.91(d, 2H), 7.82(d, 2H), 7.50(dd, 2H), 7.42-7.34(m, 4H), 3.85(q, 4H), 1.25(t, 6H).

[0434] The molecular structure of the DNDES thus obtained is shown in the following formula (1-5). In addition, the DNDES synthesized in the above synthesis example also contains isomers such as di(2-naphthyl)diethoxysilane, but even a mixture of isomers can be used directly in the subsequent polymerization reaction.

[0435]

[0436] <Synthesis of (9-phenanthrenyl)phenyldimethoxysilane (PHPDMS)>

[0437] In a 500mL four-necked flask equipped with a magnetic stirrer, a thermometer, and a dropping funnel, magnesium (6.26g, 0.258mol) and iodine (3 grains) were placed, and the system was replaced with a nitrogen atmosphere. THF 25mL and phenyltrimethoxysilane (51.06g, 0.258mol) were added to the flask, and a mixed solution of THF 100mL and 9-bromophenanthrene (64.28g, 0.250mol) was further added to the dropping funnel. Under a nitrogen stream, the dropping from the dropping funnel was started to start the preparation of the Grignard reagent and the reaction with phenyltrimethoxysilane. It took 40 minutes to drop the entire amount in the dropping funnel, and then heating with an oil bath was started, and heating reflux was performed for 3 hours. After the heating reflux was completed, air cooling and ice cooling were performed to lower the temperature to room temperature. 20mL of methanol was added while ice cooling to stop the reaction.

[0438] In another 1L flask, add a magnetic stirrer and 100mL of hexane and 300mL of toluene, and stir with a magnetic stirrer. In the stirring mixed solution of hexane and toluene, the solution after the reaction is stopped is injected, and the magnesium salt produced as a by-product in the reaction is precipitated as an off-white precipitate. The magnesium salt is filtered and separated from the reaction solution by vacuum filtration, and the residue is washed twice with 100mL of toluene heated to 70°C, washed once with 100mL of hexane at room temperature, and filtered under reduced pressure. The solvent is distilled off from the filtrate after vacuum filtration using a rotary evaporator and a vacuum pump under reduced pressure to obtain 95.10g of a crude product.

[0439] The crude product was heated to 100°C and 67 g of toluene was added. After dissolution, it was filtered while hot under reduced pressure. The filtrate was stirred with a magnetic stirrer and a magnetic stirrer and air-cooled for 100 minutes and ice-cooled for 25 minutes to obtain PHPDMS. Finally, the solid of PHPDMS was filtered out with a Kiriyama funnel, washed once with 50 mL of ice-cold hexane and twice with 100 mL, thereby obtaining 56.86 g (yield 66%) of a slightly pink white solid containing PHPDMS.

[0440] The obtained white solid was identified by NMR. As a result, the NMR spectrum data were as follows.

[0441] 1 H NMR (500 MHz, CDCl 3 ): δ8.70 (dd, 2H), 8.36 (s, 1H), 8.27 (dd, 1H), 7.95 (dd, 1H), 7.72-7.68 (m, 3H), 7.63 -7.59(m, 2H), 7.53-7.50(m, 1H), 7.43-7.40(m, 1H), 7.37-7.34(m, 2H), 3.68(s, 6H).

[0442] The molecular structure of the (9-phenanthrenyl)phenyldimethoxysilane (PHPDMS) thus obtained is shown in the following formula (1-6). In addition, the PHPDMS synthesized in the above synthesis example also contains isomers, but even a mixture of isomers can be used directly in the next polymerization reaction.

[0443]

[0444] <Synthesis of (1-naphthyl)phenyldimethoxysilane (NPDMS)>

[0445] In a 500mL four-necked flask equipped with a magnetic stirrer, a thermometer, and a dropping funnel, magnesium (9.01g, 0.371mol) and iodine (3 grains) were placed, and the system was replaced with a nitrogen atmosphere. THF 20mL and phenyltrimethoxysilane (73.53g, 0.371mol) were added to the flask, and a mixed solution of THF 100mL and 1-bromonaphthalene (74.55g, 0.360mol) was further added to the dropping funnel, and stirring was started using a magnetic stirrer. Under a nitrogen stream, dripping from the dropping funnel was started to start the preparation of the Grignard reagent and the reaction with phenyltrimethoxysilane. It took 50 minutes to drip the entire amount in the dropping funnel, and then heating with an oil bath was started, and heating reflux was performed for 2.5 hours. After the heating reflux was completed, air cooling and ice cooling were performed to lower the temperature to room temperature. 20mL of methanol was added while ice cooling to stop the reaction.

[0446] In another 500mL flask, add magnetic stirring bar and hexane 300mL, stir with magnetic stirring apparatus.In the hexane of stirring, inject the solution after reaction stops, and the magnesium salt of by-product is separated out as off-white precipitation in the reaction.By filtration under reduced pressure, magnesium salt is filtered and separated from reaction solution, and residue is cleaned 2 times with hexane 50mL, and filtration under reduced pressure is carried out.Utilize rotary evaporator to remove solvent distillation from the filtrate after filtration under reduced pressure, obtain crude product 115.84g.

[0447] The crude product was distilled under reduced pressure to obtain 90.16 g (yield 85%) of purified NPDMS (bp 143° C. / 120 Pa) as a colorless transparent oil.

[0448] The obtained oily compound was identified by NMR and GC. As a result, the NMR spectrum data was as follows, and the GC purity was 98%.

[0449] 1 H NMR (500 MHz, CDCl 3 ): δ8.25(dd, 1H), 8.00(dd, 1H), 7.94(d, 1H), 7.85(dd, 1H), 7.69-7.67(m, 2H), 7.50(dd, 1H), 7.47-7.39(m, 3H), 7.37-7.34(m, 2H), 3.65(s, 6H).

[0450] The molecular structure of the (1-naphthyl)phenyldimethoxysilane (NPDMS) thus obtained is shown in the following formula (1-7). In addition, the NPDMS synthesized in the above-mentioned synthesis example also contains isomers, but even a mixture of isomers can be used directly in the next polymerization reaction.

[0451]

[0452] <Example 1>

[0453] 17.56 g (0.040 mol) of BPEF, 14.17 g (0.041 mol) of DNDMS and 60 μmol / mol (the amount of catalyst is the relative molar number with respect to BPEF) of sodium bicarbonate as a catalyst were added into a 300 ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere.

[0454] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, depressurized to 400 hPa, reacted for 30 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the pressure was reduced to 200 hPa for 20 minutes, heated to 240°C, depressurized to 100 hPa for 10 minutes, depressurized to 50 hPa for 10 minutes, depressurized to 20 hPa for 10 minutes, depressurized to less than 1 hPa for 90 minutes.

[0455] The obtained polysilicone resin had an Mw of 17,082, a refractive index (nd) of 1.673, an Abbe number (νd) of 20.82, and a glass transition temperature (Tg) of 136°C.

[0456] <Example 2-1>

[0457] 21.56 g (0.040 mol) of BNEF, 14.17 g (0.041 mol) of DNDMS and 120 μmol / mol (the amount of catalyst is the relative molar number relative to BNEF) of sodium bicarbonate as a catalyst were added to a 300 ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere.

[0458] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, depressurized to 400 hPa, reacted for 120 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the pressure was reduced to 200 hPa, reacted for 20 minutes, heated to 240°C, depressurized to 100 hPa, reacted for 20 minutes, depressurized to 50 hPa, reacted for 10 minutes, depressurized to 20 hPa, reacted for 10 minutes, depressurized to less than 1 hPa, reacted for 90 minutes.

[0459] The obtained polysilicone resin had an Mw of 9,720, a refractive index (nd) of 1.699, an Abbe number (νd) of 18.23, and a glass transition temperature (Tg) of 152°C.

[0460] <Example 2-2>

[0461] A thermoplastic resin was obtained by substantially the same steps as in Example 2-1 except that zinc acetate was used as a catalyst instead of sodium hydrogen carbonate.

[0462] 21.56 g (0.040 mol) of BNEF, 14.17 g (0.041 mol) of DNDMS and 100 μmol / mol (the amount of catalyst is the relative molar number with respect to BNEF) of zinc acetate as a catalyst were added into a 300 ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere.

[0463] Next, the raw material mixture was heated and melted at 400 hPa and 210°C, reacted for 30 minutes, and then heated to 230°C and reacted for 60 minutes, while the methanol distilled from the reaction system was condensed and removed in a cooling tube while the reaction was carried out. Next, the pressure was reduced to 200 hPa and reacted for 20 minutes, the temperature was increased to 240°C, the pressure was reduced to 100 hPa and reacted for 10 minutes, the pressure was reduced to 50 hPa and reacted for 10 minutes, and the pressure was reduced to less than 1 hPa and reacted for 180 minutes.

[0464] The obtained polysilicone resin had an Mw of 19,510, a refractive index (nd) of 1.700, an Abbe number (νd) of 18.17, and a glass transition temperature (Tg) of 163°C.

[0465] <Example 3>

[0466] 10.78 g (0.020 mol) of BNEF, 12.54 g (0.020 mol) of 2NBN, 14.17 g (0.041 mol) of DNDMS, and 220 μmol / mol of sodium bicarbonate and 24 μmol / mol of phenoxytetraphenylphosphonium as catalysts (the amount of catalyst is the relative molar number relative to BNEF and 2NBN) were added into a 300 ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere.

[0467] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, reduced pressure to 400 hPa, reacted for 130 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the temperature was raised to 240°C for 30 minutes, reduced pressure to 200 hPa for 30 minutes, reduced pressure to 100 hPa for 30 minutes, reduced pressure to 50 hPa for 20 minutes, reduced pressure to 20 hPa for 10 minutes, and reduced pressure to less than 1 hPa for 120 minutes.

[0468] The obtained polysilicone resin had an Mw of 4,436, a refractive index (nd) of 1.719, an Abbe number (νd) of 15.74, and a glass transition temperature (Tg) of 146°C.

[0469] <Example 4>

[0470] 23.63 g (0.040 mol) of OPPFL-2EO, 14.17 g (0.041 mol) of DNDMS, 120 μmol / mol of sodium bicarbonate as a catalyst, and 6 μmol / mol of phenoxytetraphenylphosphonium (the amount of the catalyst is the relative molar number relative to OPPFL-2EO) were added to a 300 ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere.

[0471] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, depressurized to 400 hPa, reacted for 30 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the pressure was reduced to 200 hPa for 20 minutes, heated to 240°C, depressurized to 100 hPa for 10 minutes, depressurized to 50 hPa for 10 minutes, depressurized to 20 hPa for 10 minutes, depressurized to less than 1 hPa for 90 minutes.

[0472] The obtained polysilicone resin had an Mw of 6,826, a refractive index (nd) of 1.678, an Abbe number (νd) of 20.06, and a glass transition temperature (Tg) of 138°C.

[0473] <Example 5>

[0474] 21.56 g (0.040 mol) of BNEF, 5.26 g (0.021 mol) of DPDMS, 7.17 g (0.021 mol) of DNDMS, and 120 μmol / mol of sodium bicarbonate and 12 μmol / mol of phenoxytetraphenylphosphonium as catalysts (the amount of catalyst is the relative molar number relative to BNEF) were added into a 300 ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere.

[0475] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, depressurized to 400 hPa, reacted for 40 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the pressure was reduced to 200 hPa for 30 minutes, heated to 240°C, depressurized to 100 hPa for 20 minutes, depressurized to 50 hPa for 20 minutes, depressurized to 20 hPa for 10 minutes, and depressurized to less than 1 hPa for 90 minutes.

[0476] The obtained polysilicone resin had an Mw of 9,258, a refractive index (nd) of 1.688, an Abbe number (νd) of 18.93, and a glass transition temperature (Tg) of 141°C.

[0477] <Example 6>

[0478] 9.13 g (0.040 mol) of bisphenol A (BPA), 14.17 g (0.041 mol) of DNDMS, 220 μmol / mol of sodium bicarbonate as a catalyst, and 12 μmol / mol of phenoxytetraphenylphosphonium (the amount of catalyst is the relative molar number relative to BPA) were added to a 300 ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere.

[0479] Next, the raw material mixture was heated and melted at 600 hPa and 210°C, reacted for 30 minutes, then heated to 230°C, depressurized to 400 hPa, reacted for 30 minutes, and the reaction was continued while methanol distilled from the reaction system was condensed and removed in a cooling tube. Next, the temperature was raised to 240°C for 50 minutes, depressurized to 200 hPa for 20 minutes, depressurized to 100 hPa for 20 minutes, depressurized to 50 hPa for 10 minutes, depressurized to 20 hPa for 10 minutes, depressurized to less than 1 hPa for 120 minutes.

[0480] The obtained polysilicone resin had an Mw of 4,745, a refractive index (nd) of 1.664, an Abbe number (νd) of 21.09, and a glass transition temperature (Tg) of 112°C.

[0481] Furthermore, the thermoplastic resin of Example 6, unlike the other examples described above, contains a structural unit derived from BPA in addition to DNDMS, and therefore contains a structural unit represented by the formula (A-1) in which the values ​​of k1 and j1 are 0.

[0482] <Example 7>

[0483] 19.40 g (0.035 mol) of BNEF, 13.51 g (0.036 mol) of DNDES and 200 μmol / mol (the amount of catalyst is the relative molar number relative to BNEF) of zinc acetate as a catalyst were added to a 300 ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere.

[0484] Next, the raw material mixture was heated and melted under the conditions of 400 hPa and 210°C, reacted for 30 minutes, then heated to 230°C and reacted for 30 minutes, while the ethanol distilled from the reaction system was condensed and removed in a cooling tube, and the reaction was allowed to proceed. Next, the pressure was reduced to 200 hPa and reacted for 30 minutes, the temperature was increased to 240°C and reacted for 30 minutes, the pressure was reduced to 100 hPa and reacted for 20 minutes, the pressure was reduced to 50 hPa and reacted for 20 minutes, the pressure was reduced to less than 1 hPa, the temperature was increased to 260°C and reacted for 90 minutes.

[0485] The obtained polysilicone resin had an Mw of 9,229, a refractive index (nd) of 1.699, an Abbe number (νd) of 18.22, and a glass transition temperature (Tg) of 155°C.

[0486] <Example 8>

[0487] 19.40 g (0.036 mol) of BNEF, 13.81 g (0.037 mol) of D2NDES and 200 μmol / mol (the amount of catalyst is the relative molar number relative to BNEF) of zinc acetate as a catalyst were added to a 300 ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere.

[0488] Next, the raw material mixture was heated and melted under the conditions of 400 hPa and 210°C, reacted for 30 minutes, then heated to 230°C and reacted for 30 minutes, while the ethanol distilled from the reaction system was condensed and removed in a cooling tube while the reaction was carried out. Next, the pressure was reduced to 200 hPa and reacted for 20 minutes, the temperature was increased to 245°C, the pressure was reduced to 100 hPa and reacted for 10 minutes, the pressure was reduced to 50 hPa and reacted for 10 minutes, the pressure was reduced to less than 1 hPa, the temperature was increased to 260°C and reacted for 45 minutes.

[0489] The obtained polysilicone resin had an Mw of 49,339, a refractive index (nd) of 1.700, an Abbe number (νd) of 18.19, and a glass transition temperature (Tg) of 148°C.

[0490] <Example 9>

[0491] BNEF 21.56g (0.040mol), NPDMS 12.13 (0.041mol) and zinc acetate 50μmol / mol (the amount of catalyst is the relative molar number relative to BNEF) as a catalyst were added to a 300ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, reacted for 15 minutes, and then the temperature was raised to 230°C and reacted for 15 minutes. The methanol distilled from the reaction system was condensed and removed in a cooling tube while the reaction was carried out. Then, the pressure was reduced to 200hPa and the reaction was carried out for 5 minutes, the temperature was raised to 240°C, the pressure was reduced to 100hPa and the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa and the reaction was carried out for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C and the reaction was carried out for 30 minutes.

[0492] The obtained polysilicone resin had an Mw of 20,407, a refractive index (nd) of 1.689, an Abbe number (νd) of 18.87, and a glass transition temperature (Tg) of 149°C.

[0493] <Example 10>

[0494] BNEF 21.56g (0.040mol), PHPDMS 14.17 (0.041mol) and zinc acetate 50μmol / mol (the amount of catalyst is the relative molar number relative to BNEF) as a catalyst were added to a 300ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, reacted for 10 minutes, and then the temperature was raised to 230°C and reacted for 10 minutes. The methanol distilled from the reaction system was condensed and removed in a cooling tube while the reaction was carried out. Next, the pressure was reduced to 200hPa and the reaction was carried out for 5 minutes, the temperature was raised to 240°C, the pressure was reduced to 100hPa and the reaction was carried out for 5 minutes, the pressure was reduced to 50hPa and the reaction was carried out for 5 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C and the reaction was carried out for 10 minutes.

[0495] The obtained polysilicone resin had an Mw of 12,398, a refractive index (nd) of 1.699, an Abbe number (νd) of 17.99, and a glass transition temperature (Tg) of 159°C.

[0496] <Example 11>

[0497] BPEF 57.07g (0.130mol), DPC 14.20 (0.066mol), DNDMS 22.81 (0.066mol) and zinc acetate 50μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes, then the pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was continued for 20 minutes. Methanol and phenol distilled from the reaction system were condensed and removed with a cooling tube, and the reaction was continued. Next, the pressure was reduced to 200hPa, the reaction was continued for 10 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was continued for 10 minutes, the pressure was reduced to 50hPa, the reaction was continued for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was continued for 50 minutes.

[0498] The obtained polysilicone-polycarbonate resin had an Mw of 59,716, a refractive index (nd) of 1.660, an Abbe number (νd) of 21.65, and a glass transition temperature (Tg) of 143°C.

[0499] <Example 12>

[0500] BPEF 57.07g (0.130mol), DPC 19.88 (0.093mol), DNDMS 13.68 (0.040mol) and zinc acetate 50μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes, then the pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was carried out for 10 minutes. Methanol and phenol distilled from the reaction system were condensed and removed with a cooling tube, and the reaction was allowed to proceed. Next, the pressure was reduced to 200hPa, the reaction was carried out for 10 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa, the reaction was carried out for 20 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was carried out for 30 minutes.

[0501] The obtained polysilicone-polycarbonate resin had an Mw of 53,124, a refractive index (nd) of 1.653, an Abbe number (νd) of 22.23, and a glass transition temperature (Tg) of 144°C.

[0502] <Example 13>

[0503] BPEF 57.07g (0.130mol), DPC 25.82 (0.121mol), DNDMS 4.61 (0.013mol) and zinc acetate 50μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes, then the pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was carried out for 10 minutes. Methanol and phenol distilled from the reaction system were condensed and removed with a cooling tube, and the reaction was allowed to proceed. Next, the pressure was reduced to 200hPa, the reaction was carried out for 5 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa, the reaction was carried out for 5 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was carried out for 30 minutes.

[0504] The obtained polysilicone-polycarbonate resin had an Mw of 35,904, a refractive index (nd) of 1.644, an Abbe number (νd) of 22.97, and a glass transition temperature (Tg) of 145°C.

[0505] <Example 14>

[0506] BNEF 10.78g (0.020mol), DPBN 10.53g (0.020mol), DNDMS 14.17 (0.041mol) and zinc acetate 200μmol / mol (the amount of catalyst is the relative molar number relative to BNEF and DPBN) as a catalyst were added to a 300ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, reacted for 30 minutes, and then the temperature was raised to 230°C and reacted for 30 minutes. The reaction was carried out while the methanol distilled from the reaction system was condensed and removed in a cooling tube. Then, the pressure was reduced to 200hPa and the reaction was carried out for 20 minutes, the temperature was raised to 240°C, the pressure was reduced to 100hPa and the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa and the reaction was carried out for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C and the reaction was carried out for 120 minutes.

[0507] The obtained polysilicone resin had an Mw of 33,862, a refractive index (nd) of 1.705, an Abbe number (νd) of 17.06, and a glass transition temperature (Tg) of 158°C.

[0508] <Comparative Example 1>

[0509] BPEF 31.00g (0.071mol), DPDMS 18.98 (0.078mol) and cesium carbonate 15μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 990hPa and 190°C, and reacted for 30 minutes, then the temperature was raised to 210°C, the pressure was reduced to 600hPa, and the reaction was carried out for 15 minutes, while the methanol distilled from the reaction system was condensed and removed in a cooling tube, and the reaction was carried out. Next, the temperature was raised to 220°C, the pressure was reduced to 400 hPa, and the reaction was carried out for 6 minutes; the temperature was raised to 230°C, the pressure was reduced to 200 hPa, and the reaction was carried out for 10 minutes; the temperature was raised to 240°C, the pressure was reduced to 100 hPa, and the reaction was carried out for 10 minutes; the temperature was raised to 260°C, the pressure was reduced to 50 hPa, and the reaction was carried out for 20 minutes; the pressure was reduced to 20 hPa, and the reaction was carried out for 10 minutes; and the pressure was reduced to less than 1 hPa for 90 minutes.

[0510] The obtained polysilicone resin had an Mw of 46,225, a refractive index (nd) of 1.643, an Abbe number (νd) of 23.92, and a glass transition temperature (Tg) of 97°C.

[0511] <Comparative Example 2>

[0512] 70.00g (0.130mol) of BNEF, 34.25g (0.140mol) of DPDMS and 60μmol / mol of sodium bicarbonate as a catalyst (the amount of catalyst is the relative molar number relative to BNEF) were added to a 300ml four-necked flask with a stirrer, and the system was replaced under a nitrogen atmosphere. The raw materials were heated and melted at 600hPa and 210°C, and reacted for 30 minutes, then the temperature was raised to 230°C, the pressure was reduced to 400hPa, and the reaction was carried out for 90 minutes, while the methanol distilled from the reaction system was condensed and removed in a cooling tube, and the reaction was carried out. Next, the temperature was raised to 250°C, the pressure was reduced to 200hPa, the reaction was carried out for 20 minutes, the pressure was reduced to 100hPa, the reaction was carried out for 20 minutes, the pressure was reduced to 50hPa, the reaction was carried out for 10 minutes, and the pressure was reduced to less than 1hPa for 90 minutes.

[0513] The obtained polysilicone resin had an Mw of 20,890, a refractive index (nd) of 1.677, an Abbe number (νd) of 19.72, and a glass transition temperature (Tg) of 131°C.

[0514] <Comparative Example 3>

[0515] BNEF 17.51g (0.033mol), 2NBN 20.38 (0.033mol), DPDMS 17.13g (0.070mol) and sodium bicarbonate 120μmol / mol (the amount of catalyst is the relative molar number relative to BNEF and 2NBN) as a catalyst were added to a 300ml four-necked flask with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 600hPa and 210°C, and reacted for 60 minutes. The temperature was raised to 230°C, the pressure was reduced to 400hPa, and the reaction was carried out for 60 minutes. The methanol distilled from the reaction system was condensed and removed in a cooling tube while the reaction was carried out. Next, the temperature was raised to 240°C, the pressure was reduced to 200hPa, the reaction was carried out for 30 minutes, the pressure was reduced to 100hPa, the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa, the reaction was carried out for 10 minutes, and the pressure was reduced to less than 1hPa for 90 minutes.

[0516] The obtained polysilicone resin had an Mw of 13,218, a refractive index (nd) of 1.702, an Abbe number (νd) of 16.30, and a glass transition temperature (Tg) of 131°C.

[0517] <Comparative Example 4>

[0518] 15.96 g (0.070 mol) of BPA, 17.59 g (0.072 mol) of DPDMS and 15 μmol / mol (the amount of catalyst is the relative molar number relative to BPA) of cesium carbonate as a catalyst were added to a 300 ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 990 hPa and 190°C, and reacted for 30 minutes, then the temperature was raised to 210°C, the pressure was reduced to 600 hPa, and the reaction was continued for 30 minutes, while the methanol distilled from the reaction system was condensed and removed in a cooling tube, and the reaction was continued. Next, the temperature was raised to 220°C, the pressure was reduced to 400 hPa, and the reaction was carried out for 30 minutes; the temperature was raised to 230°C, the pressure was reduced to 200 hPa, and the reaction was carried out for 10 minutes; the temperature was raised to 240°C, the pressure was reduced to 100 hPa, and the reaction was carried out for 10 minutes; the temperature was raised to 260°C, the pressure was reduced to 50 hPa, and the reaction was carried out for 10 minutes; the pressure was reduced to 20 hPa, and the reaction was carried out for 10 minutes; and the pressure was reduced to less than 1 hPa for 90 minutes.

[0519] The obtained polysilicone resin had an Mw of 45,241, a refractive index (nd) of 1.618, an Abbe number (νd) of 26.90, and a glass transition temperature (Tg) of 89°C.

[0520] Moreover, the thermoplastic resin of Comparative Example 4 contains the structural unit represented by Formula (A-1) derived from BPA and having the values ​​of k1 and j1 being 0, similarly to Example 6.

[0521] <Comparative Example 5>

[0522] BPEF 57.07g (0.130mol), DPC 14.34 (0.067mol), DPDMS 16.34 (0.067mol) and zinc acetate 6μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes. The pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was carried out for 30 minutes, while methanol and phenol distilled from the reaction system were condensed and removed in a cooling tube. Next, the pressure was reduced to 200hPa, the reaction was carried out for 10 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was carried out for 10 minutes, the pressure was reduced to 50hPa, the reaction was carried out for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was carried out for 60 minutes.

[0523] The obtained polysilicone-polycarbonate resin had an Mw of 70,492, a refractive index (nd) of 1.642, an Abbe number (νd) of 23.68, and a glass transition temperature (Tg) of 123°C.

[0524] <Comparative Example 6>

[0525] BPEF 57.07g (0.130mol), DPC 20.08 (0.094mol), DPDMS 9.80 (0.040mol) and zinc acetate 6μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes. The pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was continued for 30 minutes, while methanol and phenol distilled from the reaction system were condensed and removed in a cooling tube. Next, the pressure was reduced to 200hPa, the reaction was continued for 10 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was continued for 10 minutes, the pressure was reduced to 50hPa, the reaction was continued for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was continued for 40 minutes.

[0526] The obtained polysilicone-polycarbonate resin had an Mw of 61,628, a refractive index (nd) of 1.641, an Abbe number (νd) of 23.60, and a glass transition temperature (Tg) of 133°C.

[0527] <Comparative Example 7>

[0528] BPEF 57.07g (0.130mol), DPC 25.82 (0.121mol), DPDMS 3.27 (0.013mol) and zinc acetate 6μmol / mol (the amount of catalyst is the relative molar number relative to BPEF) as a catalyst were added to a 300ml four-necked flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210°C, and reacted for 20 minutes. The pressure was reduced to 300hPa, the temperature was raised to 230°C, and the reaction was continued for 30 minutes while methanol and phenol distilled from the reaction system were condensed and removed in a cooling tube. Next, the pressure was reduced to 200hPa, the reaction was continued for 10 minutes, the pressure was reduced to 100hPa, the temperature was raised to 240°C, the reaction was continued for 10 minutes, the pressure was reduced to 50hPa, the reaction was continued for 10 minutes, the pressure was reduced to less than 1hPa, the temperature was raised to 260°C, and the reaction was continued for 23 minutes.

[0529] The obtained polysilicone-polycarbonate resin had an Mw of 58,373, a refractive index (nd) of 1.640, an Abbe number (νd) of 23.54, and a glass transition temperature (Tg) of 143°C.

[0530] [Table 1]

[0531]

[0532] The results of the examples and comparative examples show that the thermoplastic resin of the present embodiment has a high refractive index (nd) and a high Abbe number (νd). As described above, a thermoplastic resin having good properties not only in terms of refractive index but also in terms of chromatic aberration can be used in optical applications.

[0533] The molecular structures of the compounds listed in the above-mentioned Examples and Comparative Examples are shown below.

[0534] BPEF: 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene

[0535]

[0536] BNEF: 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene

[0537]

[0538] 2NBN=2DNBINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl

[0539]

[0540] DPBN: 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl

[0541]

[0542] DNDMS: di(1-naphthyl)dimethoxysilane

[0543]

[0544] DPDMS: diphenyldimethoxysilane

[0545]

Claims

1. A thermoplastic resin having a structural unit represented by the following general formula (1), characterized in that: The structural unit represented by the following general formula (1) has: AS-OSi(R 1 R 2 )O-site silane structural unit (S), and The diol structural unit (A) derived from a dihydroxy compound represented by M, In the general formula (1), R 1 and R 2 At least one of represents a polycyclic aromatic group having 10 to 30 carbon atoms which may have a substituent.

2. The thermoplastic resin according to claim 1, characterized in that: The R 1 and R 2 Based on the total molar number of the polycyclic aromatic groups, the ratio of the polycyclic aromatic groups is 30 mol% or more.

3. The thermoplastic resin according to claim 1, characterized in that: Based on the total number of moles of all the silane structural units (S) contained in the thermoplastic resin, in the general formula (1), R 1 and R 2 The ratio of the silane structural units which are all the polycyclic aromatic groups is 30 mol% or more.

4. The thermoplastic resin according to claim 1, characterized in that: In the general formula (1), R 1 and R 2 are each independently selected from the group consisting of optionally substituted naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylenyl, naphthacene and A polycyclic aromatic group.

5. The thermoplastic resin according to claim 1, characterized in that: The R 1 and R 2 Each is independently 1-naphthyl, 2-naphthyl or 9-phenanthrenyl.

6. The thermoplastic resin according to claim 1, characterized in that: The R 1 and R 2 One of them is a phenyl group which may have a substituent.

7. The thermoplastic resin according to claim 1, characterized in that: The diol structural unit (A) includes a structural unit represented by any one of the following general formulas (A-1) and (A-2), In formula (A-1) and (A-2), R 3 ~R 10 and R 30 ~R 33 each independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, Z1 and Z2 are each independently 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, X is independently a single bond or any one of the structural formulas shown in the following formula (2), In formula (2), R 11 and R 12 each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or represents R 11 and R 12 are combined with each other to form a carbon ring or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent, a and b each independently represent 0 or an integer of 1 to 5000.

8. The thermoplastic resin according to claim 1, characterized in that: The diol structural unit (A) comprises any one of the following structural units: A fluorene structural unit (F) as a structural unit derived from a fluorene ring-containing dihydroxy compound; A binaphthyl structural unit (N) which is a structural unit derived from a binaphthyl-containing dihydroxy compound; and The bisphenol structural unit (B) is derived from a bisphenol compound.

9. The thermoplastic resin according to claim 8, characterized in that: The fluorene structural unit (F) is a structural unit derived from any one of BPEF, BPPEF and BNEF.

10. The thermoplastic resin according to claim 8, characterized in that: The binaphthyl structural unit (N) contains at least a structural unit derived from 2NBN or DPBN.

11. The thermoplastic resin according to claim 8, characterized in that: The molar ratio of the fluorene structural unit (F) to the binaphthyl structural unit (N) is 30:70 to 90:

10.

12. The thermoplastic resin according to claim 1, characterized in that: The relationship between the refractive index (nd) and the Abbe number (νd) of the thermoplastic resin satisfies the following formula (I): Refractive index (nd)>-0.0078×Abbe number (νd)+1.8293…(I).

13. The thermoplastic resin according to claim 12, characterized in that: The formula (I) satisfies the following formula (I-1): -0.0080×Abbe number (νd)+1.861>refractive index (nd)>-0.0078×Abbe number (νd)+1.8293…(I-1).

14. The thermoplastic resin according to claim 1, characterized in that: The refractive index (nd) of the thermoplastic resin is 1.600 to 1.

730.

15. The thermoplastic resin according to claim 1, characterized in that: The Abbe number (νd) of the thermoplastic resin is 15.0 to 27.

0.

16. The thermoplastic resin according to claim 1, characterized in that: The Tg of the thermoplastic resin is 105-170°C.

17. A molded body, characterized in that: The thermoplastic resin according to claim 1 is included.

18. The molded article according to claim 17, wherein: The molded body is an optical lens or an optical film.

Images