WO2020080205A1

WO2020080205A1 - Thermoplastic resin composition, and optical lens or film using same

Info

Publication number: WO2020080205A1
Application number: PCT/JP2019/039730
Authority: WO
Inventors: 宗憲白武; 健太朗石原; 晃司廣瀬; 慎也池田; 加藤　宣之; 近藤　光輝; 章子鈴木; 健輔大島; 正大神田; 平川　学; 勇太中西
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2018-10-16
Filing date: 2019-10-09
Publication date: 2020-04-23
Also published as: CN112867762B; TW202035512A; CN112867762A; TWI819114B; JPWO2020080205A1; KR20210076002A

Abstract

The present invention can provide a thermoplastic resin composition containing a thermoplastic resin having a constitutional unit represented by formula (1), wherein the terminal structure of the thermoplastic resin includes a structure represented by formula (A) or formula (B), and the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is 1,000-50,000. Formula (1) (in formula (1), R represents hydrogen, a methyl group, or an ethyl group). Formula (A) (in formula (A), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylate). Formula (B)

Description

Thermoplastic resin composition and optical lens or film using the same

The present invention relates to a novel thermoplastic resin composition and an optical lens or film formed by it. A preferred embodiment of the present invention relates to a thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue and haze.

Optical glass or optical transparent resin is used as a material for optical elements used in the optical system of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are various types of materials with various refractive indices (nD) and Abbe numbers (νD), but the material cost is high. In addition to being high, it has problems of poor moldability and low productivity. In particular, processing an aspherical lens used for aberration correction requires extremely high technology and high cost, which is a major obstacle to practical use.

On the other hand, transparent lenses for optics, especially optical lenses made of thermoplastic transparent resin, have the advantages that they can be mass-produced by injection molding and that aspherical lenses are easy to manufacture. Is used as. Examples thereof include polycarbonate made of bisphenol A, polystyrene, poly-4-methylpentene, polymethylmethacrylate, and amorphous polyolefin.

However, when the transparent resin for optics is used as an optical lens, transparency, heat resistance, and low birefringence are required in addition to the refractive index and the Abbe number, so that the use location is limited by the characteristic balance of the resin. There is a weakness. For example, polystyrene has low heat resistance and high birefringence, poly-4-methylpentene has low heat resistance, and polymethylmethacrylate has low glass transition temperature, low heat resistance, and low refractive index, so its application area is limited. Polycarbonate composed of bisphenol A is not preferable because it has weak points such as large birefringence and is limited in places of use.

On the other hand, in general, when the refractive index of the optical material is high, a lens element having the same refractive index can be realized by a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, and Since it is possible to reduce the size and weight of the lens system by reducing the decentering sensitivity and the lens thickness, it is useful to increase the refractive index.

Also, in the optical design of the optical unit, it is known to correct chromatic aberration by combining and using a plurality of lenses having different Abbe numbers. For example, a lens made of an alicyclic polyolefin resin having an Abbe number of 45 to 60 and a lens made of a polycarbonate (nD = 1.59, νD = 29) resin made of bisphenol A having a low Abbe number are combined to correct chromatic aberration. Is being done.

Among the transparent optical resins that have been put to practical use for optical lenses, those with a high Abbe number include polymethylmethacrylate (PMMA) and cycloolefin polymers. In particular, cycloolefin polymers have been widely used for optical lens applications because of their excellent heat resistance and excellent mechanical properties.

Polyester and polycarbonate are examples of low Abbe number resins. For example, the resin described in Patent Document 1 is characterized by a high refractive index and a low Abbe number.

There is a difference in the coefficient of water absorption expansion between cycloolefin polymer, which has a high Abbe number, and polycarbonate resin, which is a polymer with a low Abbe number, and when the lenses of both lenses are combined to form a lens unit, it absorbs water in a usage environment such as a smartphone. When doing so, a difference occurs in the size of the lens. Due to this difference in expansion coefficient, the performance of the lens is impaired.

Patent Documents 2 to 4 describe polycarbonate copolymers containing a perhydroxydimethanonaphthalene skeleton. However, since the positions of dihydroxymethyl groups are all at the 2 and 3 positions, the strength is weak and it is suitable for optical lens applications. Is not suitable. Furthermore, the polycarbonates described in Patent Documents 2 to 4 have a low glass transition temperature (Tg), and therefore have a problem in heat resistance. For example, the polycarbonate of HOMO described in Example 1 of Patent Document 4 has a low glass transition temperature (Tg) of 125 ° C. despite having a number average molecular weight of 38,000.

International Publication No. 2014/73496 JP-A-5-70584 Japanese Patent Laid-Open No. 2-69520 JP-A-5-341124

The present invention aims to solve at least one of the above-mentioned conventional problems. Further, a preferred embodiment of the present invention aims to provide a thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze. .

As a result of intensive studies to solve the above problems, the present inventors have used decahydro-1,4: 5,8-dimethanonaphthalenediol (D-NDM) as a raw material and have a specific terminal structure. The inventors have found that a thermoplastic resin composition can solve the above problems, and have reached the present invention.

That is, the present invention relates to the following thermoplastic resin composition and an optical lens or film using the same.
<1> A thermoplastic resin composition containing a thermoplastic resin containing a structural unit represented by the following formula (1):
A terminal structure of the thermoplastic resin includes a structure represented by the following formula (A) or formula (B), and the thermoplastic resin has a polystyrene-reduced weight average molecular weight of 1,000 to 50,000. It is a plastic resin composition.

(In the formula (1), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (A), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)

<2> The thermoplastic resin composition according to <1>, wherein the thermoplastic resin further contains a structural unit represented by the following formula (2).

(In the formula (2), R represents hydrogen, a methyl group, or an ethyl group.)
<3> The thermoplastic resin composition according to <1>, wherein the thermoplastic resin further contains a structural unit represented by the following formula (3).

(In the formula (3), R represents hydrogen, a methyl group, or an ethyl group.)
<4> The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (A) is represented by the structural unit represented by the formula (1): the formula (A). The constitutional unit = 97.0: 3.00 to 99.99: 0.01, which is the thermoplastic resin composition according to any one of <1> to <3> above.
<5> The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (B) is represented by the structural unit represented by the formula (1): the formula (B). The constitutional unit is 99.00: 1.00 to 99.99: 0.01, and the thermoplastic resin composition according to any one of <1> to <3> above.
<6> The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is represented by the structural unit represented by the formula (1): the formula (2). In the thermoplastic resin composition according to <2>, the structural unit is 98.0: 2.00 to 99.99: 0.01.
<7> The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (3) is represented by the structural unit represented by the formula (1): the formula (3). The constitutional unit is 98.0: 2.00 to 99.99: 0.01, and the thermoplastic resin composition according to <3> above.
<8> The thermoplastic resin composition according to any one of <1> to <7>, wherein R is hydrogen.
<9> The thermoplastic resin composition according to any one of <1> to <8>, wherein the carboxylic acid ester in Ra is a carboxylic acid methyl ester or a carboxylic acid phenyl ester.
<10> The thermoplastic resin composition according to any one of <1> to <8>, wherein the carboxylic acid salt in Ra is sodium carboxylate.
<11> The thermoplastic resin composition according to any one of <1> to <10>, wherein the thermoplastic resin further contains a structural unit represented by the following formula (4).

(In the formula (4), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carbon atom. Selected from the group consisting of a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom; and X's each independently being branched. (A good alkylene group having 1 to 6 carbon atoms; n is each independently an integer of 0 to 5.)
<12> The thermoplastic resin composition according to any one of <1> to <11>, further containing an additive.
<13> The thermoplastic resin composition according to <12>, wherein the additive contains two or more kinds of antioxidants and a release agent.
<14> The content of the antioxidant is 0.50% by mass or less in the thermoplastic resin composition, and the content of the release agent is 0.50% by mass or less in the thermoplastic resin composition. The thermoplastic resin composition according to <13>.
<15> A compound represented by the following formula (I), a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and the following formula The thermoplastic resin composition according to any one of <1> to <14>, which contains at least one monomer selected from the group consisting of the compounds represented by (d).

(In the formula (I), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (c), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)

(In the formula (d), Rb represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)
<16> The thermoplastic resin composition according to any one of <1> to <15>, which has a specific heat capacity of 450 J / g · ° C or less.
<17> The thermoplastic resin composition according to any one of <1> to <16>, wherein the thermoplastic resin is polycarbonate, polyester carbonate, or polyester.
<18> An optical lens using the thermoplastic resin composition according to any one of <1> to <17>.
<19> A film using the thermoplastic resin composition according to any one of <1> to <17>.
<20> At least a dihydroxy compound represented by the following formula (I),
Selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d) A method of producing a thermoplastic resin composition by reacting at least one compound with
The production method is such that the total amount of the at least one compound is 10% or less with respect to the mass of the dihydroxy compound represented by the formula (I).

(In the formula (I), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (d), Rb represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)
<21> The production according to <20>, wherein the compounds represented by the formulas (a) to (d) are used in an amount of 3% or less based on the mass of the dihydroxy compound represented by the formula (I). Is the way.

According to a preferred embodiment of the present invention, it is possible to provide a thermoplastic resin composition excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze. Also, an optical lens or film produced from this resin composition can be obtained.

(A) Thermoplastic Resin Composition The thermoplastic resin of the present invention contains a structural unit represented by the following formula (1) (hereinafter referred to as “structural unit (1)”). Examples thereof include structural units derived from decahydro-1,4: 5,8-dimethanonaphthalenediol (sometimes referred to as D-NDM). As will be described later, the structural unit (1) is obtained, for example, by reacting a diol compound represented by the formula (I) with a carbonic acid diester. Preferred examples of the thermoplastic resin of the present invention include polycarbonate, polyester carbonate, and polyester. Among them, polycarbonate resin is preferred.

In formula (1), R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.

The terminal structure of the thermoplastic resin of the present invention includes a structure represented by the following formula (A) or formula (B).

In formula (A), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt. Preferable examples of the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester. Further, as the carboxylate, sodium carboxylate is preferably mentioned.

The mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (A) is the constitutional unit represented by the formula (1): the constitutional unit represented by the formula (A). = 97.0: 3.00 to 99.99: 0.01 is preferable, 99.00: 2.00 to 99.99: 0.01 is more preferable, and 99.00: 1.00 to 99.99: 0.01 is more preferable, and 99.50: 0.50 to 99.80: 0.20 is particularly preferable.
When the mass of the structural unit represented by the formula (A) is less than the above range, at least one of specific heat capacity, hue, and haze may be inferior. On the other hand, when the mass of the structural unit represented by the formula (A) is more than the above range, the hue and heat resistance of the polymer may be deteriorated.
Further, the mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (B) is represented by the constitutional unit represented by the formula (1): the formula (B). Structural unit = 99.00: 1.00 to 99.99: 0.01 is preferable, 99.00: 1.00 to 99.95: 0.05 is more preferable, and 99.50: 0.50 to 99. 90: 0.10 is more preferable, and 99.70: 0.30 to 99.90: 0.10 is particularly preferable.
When the mass of the structural unit represented by the formula (B) is less than the above range, at least one of specific heat capacity, hue, and haze may be inferior. On the other hand, when the mass of the structural unit represented by the formula (B) is more than the above range, the hue and heat resistance of the polymer may be deteriorated.
The thermoplastic resin of the present invention preferably has both the structure represented by the formula (A) and the structure represented by the formula (B) from the viewpoint of specific heat capacity.

The thermoplastic resin of the present invention may contain other structural units in addition to the resin having only the structural unit (1) and the structure represented by the formula (A) or the formula (B).
Preferred examples of the other structural unit include a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a structural unit represented by the following formula (4).

In formula (2), R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.

In formula (3), R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.

In formula (4), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carbon number. It is selected from the group consisting of a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom, and preferably selected from a hydrogen atom and a phenyl group.
In formula (4), X's each independently represent an optionally branched alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably ethylene. . Each n independently represents an integer of 0 to 5, preferably 1 or 2, and more preferably 1.

The mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (2) is as follows: Constitutional unit represented by the formula (1): Constitutional unit represented by the formula (2) = 99.00: 2.00 to 100: 0 is preferable, 99.00: 2.00 to 99.99: 0.01 is more preferable, and 99.00: 1.00 to 99.99: 0.01 is preferable. More preferably, 99.05: 0.95 to 99.99: 0.01 is particularly preferable.
When the mass of the structural unit represented by the formula (2) is in the above range, the specific heat capacity of the polymer becomes small, and the crystallinity decreases, which is preferable.
The mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (3) is as follows: Constitutional unit represented by the formula (1): Constitutional unit represented by the formula (3) = 99.00: 2.00 to 100: 0 is preferable, 99.00: 2.0 to 99.99: 0.01 is more preferable, and 99.00: 1.00 to 99.99: 0.01 is preferable. More preferably, 99.05: 0.95 to 99.99: 0.01 is particularly preferable.
When the mass of the structural unit represented by the above formula (3) is in the above range, the specific heat capacity of the polymer becomes small and the crystallinity decreases, which is preferable.
The mass ratio of the constitutional unit represented by the formula (1) and the constitutional unit represented by the formula (4) is as follows: Constitutional unit represented by the formula (1): Constitutional unit represented by the formula (4) = 99: 1 to 1:99 is preferable, 90:10 to 10:90 is more preferable, 75:25 to 50:50 is further preferable, and 70:30 to 60:40 is particularly preferable. When the mass of the structural unit represented by the above formula (4) is in the above range, the moldability is improved, and for example, the strength of the molded body such as impact strength is improved, which is preferable.

The thermoplastic resin of the present invention may contain other structural units in addition to the above structural units.
Other constituent units that may be included include constituent units obtained by reacting a diol compound other than the formula (I) with a carbonic acid diester. Examples of the diol compound other than the formula (I) include bisphenol A and bisphenol AP. , Bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, 9,9-bis (4- (2 -Hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl Phenyl) Fluo , 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9- Examples thereof include bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene. Among these, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene is preferable.

The thermoplastic resin composition of the present invention is represented by the compound represented by the following formula (I), the compound represented by the following formula (a), the compound represented by the following formula (b), and the following formula (c). And a compound represented by the following formula (d), at least one of which is selected from the group consisting of compounds represented by the following formula (d), thereby reducing specific heat capacity, decreasing crystallinity, and reducing haze: It is preferable because the fluidity when melted for the molecular weight is improved and precision molding of an optical molded article or the like is facilitated.

In formula (I), R represents hydrogen, a methyl group, or an ethyl group, and preferably R represents hydrogen.

In formula (c), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt. Preferable examples of the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester. Further, as the carboxylate, sodium carboxylate is preferably mentioned.

In the formula (d), Rb represents hydrogen, carboxylic acid, carboxylic acid ester, or carboxylic acid salt. Preferable examples of the carboxylic acid ester include carboxylic acid methyl ester and carboxylic acid phenyl ester. Further, as the carboxylate, sodium carboxylate is preferably mentioned.

The polystyrene equivalent weight average molecular weight (Mw) of the thermoplastic resin of the present invention is 1,000 to 50,000. The weight average molecular weight (Mw) in terms of polystyrene is preferably 10,000 to 40,000, and more preferably 20,000 to 30,000. If the Mw is less than 1,000, the optical lens becomes brittle, which is not preferable. When the Mw is more than 50,000, the melt viscosity becomes high, so that it is difficult to remove the resin after production, and further, the fluidity is deteriorated and injection molding in a molten state becomes difficult, which is not preferable.

The thermoplastic resin composition of the present invention may contain additives. The additive preferably contains two or more kinds of antioxidants and a release agent. The reason is that the antioxidant effect and the releasability are synergistically improved when two or more kinds of antioxidants and a release agent are added, rather than when they are added one by one.

Antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-ter -Butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-dimethyl-2- [β- Examples include (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane.
The content of the antioxidant in the thermoplastic resin composition is preferably 0.50% by mass or less, more preferably 0.10 to 0.40% by mass, and 0.20 to 0. It is particularly preferably 40% by mass.

As the release agent, it is preferable that 90% by weight or more thereof is composed of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include an ester of monohydric alcohol and fatty acid, and a partial ester or total ester of polyhydric alcohol and fatty acid. The ester of monohydric alcohol and fatty acid is preferably ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. As the partial ester or total ester of polyhydric alcohol and fatty acid, partial ester or total ester of polyhydric alcohol having 1 to 25 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms is preferable.

Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate and isopropyl palmitate. As a partial ester or a full ester of a polyhydric alcohol and a saturated fatty acid, stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, Diesters such as pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate. Examples thereof include all-esters or partial-esters of pentaerythritol.
The content of the release agent in the thermoplastic resin composition is preferably 0.50% by mass or less, more preferably 0.01 to 0.10% by mass, and 0.03 to 0. It is particularly preferable that the content is 05% by mass.

Further, to the thermoplastic resin composition of the present invention, as other additives, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, a bluing agent or an antibacterial agent is added. You may.

(B) Method for producing diol compound represented by formula (I) The diol compound represented by the above formula (I) includes dicyclopentadiene or cyclopentadiene and an olefin having a functional group, as shown in WO2017 / 175693. It can be synthesized as a raw material.

(C) Method for producing thermoplastic resin The thermoplastic resin of the present invention contains at least a dihydroxy compound represented by the following formula (I):
Selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d) A method of producing a thermoplastic resin composition by reacting at least one compound with
It can be produced by a production method in which the total amount of the at least one compound is 10% or less based on the mass of the dihydroxy compound represented by the formula (I).
The total amount of the at least one compound is preferably 0.005 to 3.0%, and preferably 0.1 to 1.0, with respect to the mass of the dihydroxy compound represented by the formula (I). Is more preferable, and 0.1 to 0.5% is particularly preferable. When the total amount of the at least one compound is more than 10% with respect to the mass of the dihydroxy compound represented by the formula (I), the reactivity during polymerization is lowered, the molecular weight does not increase, and the pellets are stable. Cannot be transformed. Even if it can be pelletized, it cannot be stably molded, and a desired molded product cannot be obtained in a mold. In particular, in the formula (a), the formula (b), and the formula (c), when Ra is hydrogen, the reactivity during the polymerization is lowered, and the molecular weight is difficult to increase. When Ra in the formula (c) is a carboxylic acid or a carboxylic acid ester, the hue of the resulting resin tends to deteriorate, and the heat resistance tends to deteriorate.
Further, it is preferable to use each of the compounds represented by the formulas (a) to (d) in an amount of 3% or less based on the mass of the dihydroxy compound represented by the formula (I).

When the thermoplastic resin of the present invention is a polycarbonate resin, for example, a diol compound represented by the formula (I), at least one of the compounds represented by the formulas (a) to (d), and a carbonic acid diester are used as raw materials. It can be produced by a melt polycondensation method. The diol compound represented by the formula (I) has a mixture of isomers in which the hydroxymethyl group is in the 2,6-position and isomers in the 2,7-position. The mass ratio of these isomers is 2,6-position isomer: 2,7-position isomer = 0.1: 99.9 to 99.9: 0.1. From the viewpoint of resin physical properties such as resin strength, tensile elongation, and appearance of a molded product, 2,6-position isomer: 2,7-position isomer = 1.0: 99.0 to 99.0: 1. 0, preferably 2,6-position isomer: 2,7-position isomer = 20: 80 to 80:20, more preferably 2,6-position isomer: 2,7-position isomer It is particularly preferable that the isomers = 50: 50 to 80:20. Further, other diol compounds may be used together. In this reaction, the polycondensation catalyst can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst composed of both.

Examples of carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Among these, diphenyl carbonate is particularly preferable from the viewpoint of reactivity and purity. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, based on 1 mol of the diol component. The molecular weight of the polycarbonate resin is controlled by adjusting this molar ratio.

Examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals. Sodium carbonate and sodium hydrogen carbonate are preferable from the viewpoints of catalytic effect, price, distribution amount, influence on the hue of resin, and the like.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkaline earth metal compounds.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxide and salts thereof, amines and the like.

As the transesterification catalyst, salts of zinc, tin, zirconium and lead are preferably used, and these can be used alone or in combination. Further, it may be used in combination with the above-mentioned alkali metal compound or alkaline earth metal compound.

These catalysts are used in a ratio of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ mol, based on 1 mol of the total amount of the diol compound. .

The melt polycondensation method is a method of performing melt polycondensation using the above-mentioned raw materials and catalysts while removing by-products by transesterification under heating under normal pressure or reduced pressure. The reaction is generally carried out in multiple stages of two or more stages.

Specifically, the first stage reaction is carried out at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Then, the reaction temperature is raised while raising the degree of vacuum in the reaction system to react the diol compound with the carbonic acid diester, and finally polycondensation is carried out under a reduced pressure of 1 mmHg or less at a temperature of 200 to 350 ° C for 0.05 to 2 hours. Perform the reaction. Such a reaction may be carried out continuously or batchwise. The reactor used when carrying out the above reaction is a vertical type equipped with an anchor type stirring blade, Maxblend stirring blade, helical ribbon type stirring blade, etc., but equipped with paddle blades, lattice blades, eyeglass blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reactor in which these are appropriately combined in consideration of the viscosity of the polymer.

In the method for producing a thermoplastic resin of the present invention, the catalyst may be removed or deactivated after the completion of the polymerization reaction in order to maintain thermal stability and hydrolysis stability. Generally, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. From the viewpoints of deactivating effect, hue and stability of resin, it is preferable to use butyl p-toluenesulfonate. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times the molar amount of the catalyst. When the amount is less than 0.01 times the molar amount of the catalyst, the deactivating effect becomes insufficient, which is not preferable. On the other hand, if the amount is more than 50 times the molar amount of the catalyst, the heat resistance is lowered and the molded product is easily colored, which is not preferable.

After deactivating the catalyst, a step of devolatilizing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided. For this purpose, paddle blades, lattice blades, glasses A horizontal device provided with a stirring blade having excellent surface renewal ability, such as a blade, or a thin film evaporator is preferably used.

The thermoplastic resin of the present invention is desired to have a foreign matter content as small as possible, and thus the molten raw material and the catalyst liquid are preferably filtered. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Further, filtration of the produced resin with a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. In addition, the step of collecting the resin pellets must be in a low dust environment, and is preferably class 1000 or less, more preferably class 100 or less.

(D) Physical Properties of Thermoplastic Resin The thermoplastic resin of a preferred embodiment of the present invention is excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze.
The specific heat capacity of the thermoplastic resin of the present invention is preferably 450 J / g · ° C. or less, more preferably 1 to 400 J / g · ° C. G, further preferably 50 to 300 J / g · ° C., further preferably 100 to 300 J / g · ° C. Is more preferable, and 200 to 300 J / g · ° C. is particularly preferable. When the specific heat capacity is 450 J / g · ° C. or less, the crystallinity is lowered, the physical properties such as haze are reduced, and the hue represented by YI tends to be good.
The glass transition temperature (Tg) of the thermoplastic resin of the present invention is preferably 95 to 180 ° C, more preferably 110 to 160 ° C, and particularly preferably 120 to 160 ° C. If the Tg is lower than 95 ° C., the operating temperature range of the lens or camera becomes narrow, which is not preferable. Further, if the temperature exceeds 180 ° C., the molding conditions for injection molding become strict, which is not preferable.

The thermoplastic resin of the present invention preferably has a refractive index of 1.50 to 1.65 measured by the method of JIS-K-7142 after molding, and more preferably 1.53 to 1.58.
The thermoplastic resin of the present invention has an Abbe's number of 25 or more, preferably 35 or more, more preferably 45 or more, measured by the method of JIS-K-7142 after molding. The upper limit of the Abbe number is about 55.
The hue (YI) of the thermoplastic resin of the present invention is preferably 0.1 to 5.0, more preferably 1.0 to 3.5, and particularly preferably 2.0 to 3.0.
The haze (Hz) of the thermoplastic resin of the present invention is preferably 0.1 to 0.5, more preferably 0.1 to 0.2.

In the thermoplastic resin of the present invention, phenol produced during production and carbonic acid diester remaining without reaction may be present as impurities. The phenol content in the thermoplastic resin is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, and 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. Is particularly preferred. The content of carbonic acid diester in the thermoplastic resin is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. By adjusting the amounts of phenol and carbonic acid diester contained in the thermoplastic resin, a resin having physical properties suitable for the purpose can be obtained. The phenol and carbonic acid diester contents can be adjusted appropriately by changing the polycondensation conditions and equipment. It can also be adjusted depending on the conditions of the extrusion process after polycondensation.

When the content of phenol or carbonic acid diester exceeds the above range, the strength of the obtained resin molded product may be reduced, and problems such as odor may occur. On the other hand, when the content of phenol or carbonic acid diester is less than the above range, the plasticity at the time of melting the resin may decrease.

(E) Optical Lens The optical lens of the present invention can be obtained by injection molding the above-mentioned thermoplastic resin of the present invention into a lens shape by an injection molding machine or an injection compression molding machine. The molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 300 ° C, more preferably 180 to 290 ° C. The injection pressure is preferably 50 to 1700 kg / cm ² .

In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment must also be a low dust environment, and is preferably class 1000 or lower, more preferably class 100 or lower.

The optical lens of the present invention is preferably used in the form of an aspherical lens, if necessary. Since an aspherical lens can reduce the spherical aberration to substantially zero with one lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the production cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. The astigmatism of the aspherical lens is preferably 0 to 15 mλ, more preferably 0 to 10 mλ.

The thickness of the optical lens of the present invention can be set in a wide range according to the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm. If necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens of the present invention. The antireflection layer may be a single layer or a multilayer, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride. Of these, more preferred are silicon oxide and zirconium oxide, and even more preferred is a combination of silicon oxide and zirconium oxide. The antireflection layer is not particularly limited in the combination of single layer / multilayer and the combination of components and thickness thereof, but preferably has a two-layer structure or a three-layer structure, particularly preferably a three-layer structure. The antireflection layer as a whole is preferably formed with a thickness of 0.0017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 μm, particularly preferably 1 to 2 μm.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
<Manufacture of raw materials>
Mixture Im
A mixture Im was obtained in the same manner as in “Monomer Synthesis Example 1” except that distillation purification was not performed in “Monomer Synthesis Example 1” shown in WO2017 / 175693. In addition to the main product, Compound Ip, this mixture Im contained the compounds a, b, c-1, c-2, and d as impurities as impurities in the following contents. Was there. The content of the monomer was measured by gas chromatography (manufacturing equipment: Shimadzu Corporation GC-2010 Plus) using a mixture of 1 mass% methanol solution under a temperature-raising vaporization method of 50 to 300 ° C. It is the value that was performed. The same applies hereinafter.
Compound a: 5.0000 mass%
Compound b: 3.0000 mass%
Compound c-1: 2.0000% by mass
Compound c-2: 1.0000 mass%
Compound d: 1.0000 mass%

Mixture I-1
A mixture I-1 was obtained by the same method as "monomer synthesis example 1" shown in WO2017 / 175693 (distillation purification x 1 time). In addition to the main product, Compound Ip, this mixture I-1 also contained the compounds a, b, c-1, c-2, and d as impurities as impurities in the following contents. Was there.
Compound a: 1.4000 mass%
Compound b: 0.5000 mass%
Compound c-1: 1.8000 mass%
Compound c-2: 0.0100% by mass
Compound d: 0.0100 mass%

Mixture I-2
The mixture I-1 obtained above was distilled again (distillation purification: twice in total) to obtain a mixture I-2. This mixture I-2 contained, as impurities, the compounds a, b, c-1 and c-2, which were monomers, in addition to the main product, the compound Ip, in the following contents.
Compound a: 0.9900 mass%
Compound b: 0.4300% by mass
Compound c-1: 0.6100% by mass
Compound c-2: 0.0100% by mass
Compound d: below detection limit (less than 0.0001 mass%)

The mixture I-2 obtained above was distilled again (distillation purification: 3 times in total) to obtain a mixture I-3. This mixture I-3 contained, as impurities, the compounds a, b and c-1 which were the monomers, in addition to the main product, the compound Ip, in the following contents.
Compound a: 0.3400 mass%
Compound b: 0.1100% by mass
Compound c-1: 0.0200 mass%
Compound c-2: below detection limit (less than 0.0001 mass%)
Compound d: below detection limit (less than 0.0001 mass%)

Compound Ip
By repeating the distillation purification of the mixture I-1 obtained above until the monomers a, b, c-1, c-2, and d are below the detection limit (distillation purification: 6 times in total). , Pure compound Ip was obtained. The detection limits of the compounds a, b, c-1, c-2, and d, which are impurity monomers, were each 0.0001 mass%.
The compounds a, b, c-1, c-2, and d were fractionated during the distillation purification when the compound Ip was obtained, and fractionated by a fractionation column.

<Measurement method of weight average molecular weight (Mw)>
The polystyrene-converted weight average molecular weight was determined from the calibration curve of standard polystyrene prepared in advance. That is, a calibration curve was created using standard polystyrene ("PStQuick MP-M" manufactured by Tosoh Corporation) of known molecular weight (molecular weight distribution = 1), and the elution time and molecular weight value of each peak were plotted from the measured standard polystyrene. Then, approximation by a cubic equation was performed to obtain a calibration curve. Mw was calculated from the following formula.
Mw = Σ (Wi × Mi) ÷ Σ (Wi)
Here, i represents the i-th division point when the molecular weight M is divided, Wi represents the i-th weight, and Mi represents the i-th molecular weight. The molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve. HLC-8320GPC manufactured by Tosoh Corporation was used as a GPC device, one TSKguardcolumn SuperMPHZ-M was used as a guard column, and three TSKgel SuperMultiporeHZ-M were connected in series as an analytical column. Other conditions are as follows.
Solvent: HPLC grade tetrahydrofuran Injection volume: 10 μL
Sample concentration: 0.2 w / v% HPLC grade chloroform solution Solvent flow rate: 0.35 ml / min
Measurement temperature: 40 ° C
Detector: RI

<Method of measuring refractive index nD and Abbe number νD>
The obtained thermoplastic resin composition was press-molded (molding conditions: 200 ° C., 100 kgf / cm ² , 2 minutes) on a disc having a diameter of 40 mm and a thickness of 3 mm, cut out at a right angle, and measured by KPR-200 manufactured by Karnew.
<Specific heat capacity (J / g * ° C) measurement method>
It was measured by a differential scanning calorimeter (DSC) based on JIS K7123-1987. Hitachi High-Tech Science X-DSC7000 was used as the calorimeter.
<Glass transition temperature (Tg)>
Based on JIS K7121-1987, it was measured by a differential scanning calorimeter (DSC). As the analyzer, Hitachi High-Tech Science X-DSC7000 was used.
<Method of measuring hue (YI) and haze (Hz)>
Using an injection molding machine SH50 manufactured by Sumitomo Heavy Industries, Ltd., injection molding was carried out at a cylinder temperature of 260 ° C. and a mold temperature of 30 ° C. lower than the glass transition temperature of the resin to obtain a 3 mm thick disc. Hue (YI) and haze (Hz) were measured using this disc.
The hue (YI) was measured by SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the haze (Hz) was measured by NDH2000 manufactured by Nippon Denshoku.

(Example 1)
As raw materials, the compound Ip obtained above (endo form: exo form = 25: 75): 1.0000 mol (222.3336 g), compound a represented by the above structural formula: 0.0168 mol (3 .2343 g), compound b: 0.0050 mol (1.1551 g), compound c-1: 0.0189 mol (4.1584 g), compound c-2: 0.0005 mol (0.1155 g), compound d: ² liters of 0.0001 mol (0.0231 g), sodium hydrogen carbonate: 1 × 10 ^-2 mol (0.840000 g) and diphenyl carbonate: 1.0363 mol (222.0000 g) with a stirrer, a heating device and a distillation device It was placed in a reactor and the reactor was replaced with nitrogen gas. At this point, the reaction was started, and the temperature was raised to 210 ° C. over 1 hour under 760 Torr. Stirring was started when the raw materials were visually dissolved. Phenol was recovered in the distillation device at 180 ° C. 1 hour and 20 minutes after the start of the reaction, phenol started to be collected in the distillation apparatus. After 1 hour and 30 minutes from the start of the reaction, the pressure was reduced from 760 Torr to 200 Torr in 10 minutes, and at the same time, the temperature was heated to 215 ° C. Two hours after the start of the reaction, the temperature was raised to 220 ° C, and 2 hours and 30 minutes after the start of the reaction, the pressure was reduced to 150 Torr over 30 minutes, and at the same time, the temperature was raised to 250 ° C. Subsequently, the pressure was reduced to 1 Torr and the pressure was maintained for 30 minutes. After introducing nitrogen gas into the reactor and returning the pressure inside the reactor to normal pressure, the obtained polycarbonate resin was pelletized, and then the pellet was dried at 110 ° C. for 3 hours to obtain a polycarbonate resin A.
Separately, as raw materials, BPEF represented by the following structural formula: 1.000 mol (438.52 g), sodium hydrogencarbonate: 1 × 10 ⁻⁶ mol (0.084 mg, added as a 1% by mass aqueous solution) and diphenyl carbonate. : Polycarbonate resin W was obtained by reacting and pelletizing in the same manner as the above-mentioned polycarbonate resin A except that 1.020 mol (218.50 g) was used. Subsequently, the pellets were dried at 110 ° C. for 3 hours.

Polycarbonate resin A pellets and polycarbonate resin W pellets were mixed in a mass ratio of polycarbonate resin A: polycarbonate resin W = 68: 32, and glycerin mono that was a release agent was added to the polycarbonate resin composition as an additive. Stearate (Riken Vitamin Co., Ltd .; Rikemal S-100A) 0.20% by mass, antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ( ADEKA CORPORATION; ADEKA STAB AO-60) 0.10% by weight, antioxidant 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10 -Tetraoxa-3,9-diphosphaspiro [5.5] undecane (A Co., Ltd. EKA; ADK STAB PEP-36) After impregnating the pellets to 0.05% by mass, it is heated at 280 ° C by a vent-type twin-screw extruder (IPEC manufactured by Niigata Iron Works Co., Ltd .; complete meshing and rotating in the same direction). And melt mixed. The physical properties of the obtained polycarbonate resin composition are shown in Table 1.

(Examples 2 to 11, Comparative Examples 1 and 2)
Polycarbonate resins B to K were obtained in the same manner as in Example 1 except that the raw materials and the charged amounts shown in Table 2 were changed.
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the polycarbonate resins B to K were used instead of the polycarbonate resin A and the additives and the amounts of the additives shown in Table 1 were used instead. The physical properties of the obtained polycarbonate resin composition are shown in Table 1.

The additives in Tables 1 and 2 are as follows.
S-100A: Glycerin monostearate (Riken Vitamin Co., Ltd .; Rikemar S-100A) which is a release agent
B-100A: Glycerin monobehenate as a release agent (manufactured by Riken Vitamin Co., Ltd .; Rikemar B-100A)
Poem M-100: Glycerin monocaprylate (Riken Vitamin Co., Ltd .; Poem M-100) as a release agent
Poem M-300: Glycerin monolaurate as a release agent (Riken Vitamin Co., Ltd .; Poem M-300)
AO-60: Antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation; ADEKA STAB AO-60)
AO-30: [4,4 ′, 4 ″-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol) which is an antioxidant] (manufactured by ADEKA Corporation; ADEKA STAB) AO-30)
AO-50: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate which is an antioxidant (manufactured by ADEKA Corporation; ADEKA STAB AO-50)
PEP-36: Antioxidant 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] Undecane (made by ADEKA Corporation; ADEKA STAB PEP-36)
HP-10: 2,2'-methylenebis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite which is an antioxidant (manufactured by ADEKA Corporation; ADEKA STAB HP-10)
ADEKA STAB 2112: Tris (2,4-di-tert-butylphenyl) phosphite which is an antioxidant (manufactured by ADEKA Corporation; ADEKA STAB 2112)

(Example A)
The same procedure as in Example 1 was repeated except that, instead of the compound Ip, the mixture I-1 obtained above was 222.33 g, sodium hydrogencarbonate was 8.4 mg, and diphenyl carbonate was 221.90 g. A polycarbonate resin composition was obtained. Table 3 shows the physical properties of the obtained polycarbonate resin composition.

(Example A-1 to Example C-2)
The same procedure as in Example A was carried out except that the raw materials and the charged amounts shown in Table 3 were changed. Table 3 shows the physical properties of the obtained polycarbonate resin composition.

According to the preferred embodiment of the present invention, an optical lens excellent in at least one of Abbe number, refractive index, specific heat capacity, glass transition temperature (heat resistance), hue, and haze can be obtained. The optical lens of the present invention can be injection-molded, has high productivity, and is inexpensive. Therefore, it can be used in fields where expensive high-Abbe glass lenses have been conventionally used, such as cameras, telescopes, binoculars, and television projectors. It is useful. Further, since the difference in water absorption between the high Abbe lens and the low Abbe lens becomes small, it is particularly suitable for a small optical lens unit. Further, according to the present invention, a high Abbe aspherical lens, which is technically difficult to process with a glass lens, can be easily obtained by injection molding, which is extremely useful.

Claims

A thermoplastic resin composition containing a thermoplastic resin containing a structural unit represented by the following formula (1),
A terminal structure of the thermoplastic resin includes a structure represented by the following formula (A) or formula (B), and the thermoplastic resin has a polystyrene-reduced weight average molecular weight of 1,000 to 50,000. Plastic resin composition.

(In the formula (1), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (A), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin further contains a structural unit represented by the following formula (2).

(In the formula (2), R represents hydrogen, a methyl group, or an ethyl group.)
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin further contains a structural unit represented by the following formula (3).

(In the formula (3), R represents hydrogen, a methyl group, or an ethyl group.)
The mass ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (A) is represented by the structural unit represented by the formula (1): the structural unit represented by the formula (A). The thermoplastic resin composition according to any one of claims 1 to 3, wherein: 97.0: 3.00 to 99.99: 0.01.
The mass ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (B) is represented by the structural unit represented by the formula (1): the structural unit represented by the formula (B). The thermoplastic resin composition according to any one of claims 1 to 3, wherein: 99.00: 1.00 to 99.99: 0.01.
The mass ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is represented by the structural unit represented by the formula (1): the structural unit represented by the formula (2). The thermoplastic resin composition according to claim 2, wherein: 98.00: 2.00 to 99.99: 0.01.
The mass ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (3) is represented by the structural unit represented by the formula (1): the structural unit represented by the formula (3). The thermoplastic resin composition according to claim 3, wherein: 98.0: 2.00 to 99.99: 0.01.
The thermoplastic resin composition according to any one of claims 1 to 7, wherein R is hydrogen.
The thermoplastic resin composition according to any one of claims 1 to 8, wherein the carboxylic acid ester in Ra is a carboxylic acid methyl ester or a carboxylic acid phenyl ester.
The thermoplastic resin composition according to any one of claims 1 to 8, wherein the carboxylate salt in Ra is sodium carboxylate.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin further contains a structural unit represented by the following formula (4).

(In the formula (4), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carbon atom. Selected from the group consisting of a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom; and X's each independently being branched. (A good alkylene group having 1 to 6 carbon atoms; n is each independently an integer of 0 to 5.)
The thermoplastic resin composition according to any one of claims 1 to 11, further comprising an additive.
The thermoplastic resin composition according to claim 12, wherein the additive contains two or more kinds of antioxidants and a release agent.
The content of the antioxidant is 0.50% by mass or less in the thermoplastic resin composition, and the content of the release agent is 0.50% by mass or less in the thermoplastic resin composition, The thermoplastic resin composition according to claim 13.
A compound represented by the following formula (I), a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a following formula (d) The thermoplastic resin composition according to claim 1, comprising at least one monomer selected from the group consisting of compounds represented by:

(In the formula (I), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (c), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)

(In the formula (d), Rb represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)
The thermoplastic resin composition according to any one of claims 1 to 15, which has a specific heat capacity of 450 J / g · ° C or less.
The thermoplastic resin composition according to any one of claims 1 to 16, wherein the thermoplastic resin is polycarbonate, polyester carbonate, or polyester.
An optical lens using the thermoplastic resin composition according to any one of claims 1 to 17.
A film using the thermoplastic resin composition according to any one of claims 1 to 17.
At least a dihydroxy compound represented by the following formula (I):
Selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d) A method of producing a thermoplastic resin composition by reacting at least one compound with
The production method, wherein the total amount of the at least one compound is 10% or less based on the mass of the dihydroxy compound represented by the formula (I).

(In the formula (I), R represents hydrogen, a methyl group, or an ethyl group.)

(In the formula (c), Ra represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)

(In the formula (d), Rb represents hydrogen, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid salt.)
21. The production method according to claim 20, wherein the compounds represented by the formulas (a) to (d) are used in an amount of 3% or less with respect to the mass of the dihydroxy compound represented by the formula (I).