CN115087648A

CN115087648A - Compound, thermoplastic resin, optical member, and optical lens

Info

Publication number: CN115087648A
Application number: CN202180013555.8A
Authority: CN
Inventors: 杉原裕介; 林宽幸; 大谷鹰士; 藤通昭
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2020-02-18
Filing date: 2021-02-18
Publication date: 2022-09-20
Anticipated expiration: 2041-02-18
Also published as: TW202138360A; WO2021166990A1; JP7416196B2; JPWO2021166990A1

Abstract

The present disclosure relates to: a compound which, when used as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond, can give a thermoplastic resin having a high refractive index, good moldability, and no risk of mold corrosion; thermoplastic resins obtained from the above compounds; and an optical member and an optical lens comprising the above thermoplastic resin. The compounds of the present disclosure are represented by the following formula (f); the thermoplastic resin of the present disclosure includes a structural unit based on the above compound; the optical member and the optical lens of the present disclosure comprise the aboveA thermoplastic resin. B is ¹ And B ² : a polymerization reactive group; l is ¹ And L ² : an alkylene group having 1 to 10 carbon atoms, which may have a substituent; m, n: 1 to 4; non-bonded (L) in carbon atoms of substitution positions 1 to 6,8 to 13 ¹ O) _m Or (L) ² O) _n A hydrogen atom or the like is bonded to the carbon atom(s) of (3).

Description

Compound, thermoplastic resin, optical member, and optical lens

Technical Field

The present disclosure relates to a compound, a thermoplastic resin, an optical member, and an optical lens.

The present application is based on the priority claim of Japanese patent application No. 2020-025216 filed by the Japanese patent office on 2/18/2020, the contents of which are hereby incorporated by reference.

Background

Optical glass and optical resin are used as materials for optical lenses used in various optical products such as cameras, video cameras, mobile phones with cameras, television phones, and intercom doorbells with cameras.

Optical glass and the like can realize various optical characteristics required and have excellent environmental resistance. However, optical glass and the like have problems of poor processability and low productivity.

On the other hand, the optical resin has an advantage that it can be mass-produced by injection molding. Because of this advantage, for example, an optical lens formed of an optical resin such as polycarbonate is used as a camera lens.

As a resin for lenses, a polycarbonate obtained by bonding bisphenol a with a carbonate is widely used. The refractive index of the polycarbonate was 1.586.

In recent years, development of a resin having a high refractive index has been demanded in accordance with reduction in thickness, size, and size of products. In general, when the refractive index of an optical material is high, lens elements having the same refractive index can be expressed by a surface having a smaller curvature, and thus aberration generated by the surface can be reduced. As a result, the number of lenses can be reduced, the decentering sensitivity of the lens can be reduced, or the thickness of the lens can be reduced to reduce the weight.

However, generally, when the refractive index of the resin is increased, the glass transition temperature of the resin is also increased, and the molding processability tends to be lowered. Therefore, a resin having a high refractive index and excellent moldability has been studied.

Patent document 1 discloses an optical lens formed of a polycarbonate obtained by carbonate-bonding 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene.

Patent document 2 discloses a lens formed from a composition containing a polycarbonate obtained by carbonate-bonding 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene and 3, 11-dihydroxyethoxynaphthothiophene.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2007 and 57916

Patent document 2: japanese patent No. 6014788

Disclosure of Invention

Problems to be solved by the invention

In patent document 1, the refractive index of a polycarbonate obtained by carbonate-bonding 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene is 1.639, and a further increase in refractive index is required.

In patent document 2, the polycarbonate has a dinaphthothiophene skeleton, and therefore the refractive index thereof is higher than that of the polycarbonate of patent document 1. However, according to the studies of the present inventors, sulfur dioxide may be generated in the vicinity of the molding temperature of the polycarbonate. This sulfur dioxide is an acidic substance and thus causes corrosion of the mold. Therefore, the polycarbonate of patent document 2 is difficult to reuse the mold during molding, and is poor in practicability.

The purpose of this disclosure is to provide: a compound which, when used as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond, can give a thermoplastic resin having a high refractive index, good moldability, and no risk of mold corrosion; a thermoplastic resin having a high refractive index, good moldability, and no risk of corrosion of a mold; and an optical member and an optical lens comprising the above thermoplastic resin.

Means for solving the problems

The present disclosure includes the following embodiments [1] to [17 ].

[1] A compound represented by the following formula (f).

[ solution 1]

In the formula (f), B ¹ And B ² Each independently represents a polymerization reactive group;

L ¹ and L ² Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

(L ¹ O) _m bonded to any one of the carbon atoms of substitution position numbers 1 to 6;

(L ² O) _n bonded to any one of carbon atoms of substitution position numbers 8-13;

non-bonded (L) in carbon atoms of substitution positions 1 to 6,8 to 13 ¹ O) _m Or (L) ² O) _n Each of which is independently bonded with a hydrogen atom or an optional substituent.

[2]Such as [1]]Wherein, B is as defined above ¹ And B ² Being a hydroxyl group, the compound is represented by the following formula (f 1).

[ solution 2]

In the formula (f1), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The optional substituents for the carbon atoms at the bonding positions and substitution positions 1 to 6 and 8 to 13 in (a) are the same as those in the above formula (f).

[3]Such as [1]]Wherein, B is as defined above ¹ And B ² Being an ester group, the compound is represented by the following formula (f 2).

[ solution 3]

In the formula (f2), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The bonding positions and optional substituents of the carbon atoms of the substitution position numbers 1 to 6,8 to 13 are the same as those of the formula (f);

B ³ and B ⁴ Each independently represents a hydroxyl group, an organic substituent having 1 to 10 carbon atoms, or a halogen atom.

[4]Such as [1]]Wherein, B is as defined above ¹ And B ² Being a hydroxyl ester group, the compound is represented by the following formula (f 3).

[ solution 4]

In the formula (f3), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The bonding positions and optional substituents of the carbon atoms of the substitution position numbers 1 to 6,8 to 13 are the same as those of the formula (f);

B ⁵ and B ⁶ Each independently represents an alkylene group having 1 to 10 carbon atoms with or without a substituent, with or withoutAn arylene group having 4 to 10 carbon atoms as a substituent, or an aralkylene group having 6 to 12 carbon atoms with or without a substituent.

[5]Such as [1]]～[4]A compound of any one of the above, wherein L is ¹ And L ² Each independently represents an alkylene group having 1 to 10 carbon atoms with or without a substituent.

[6] The compound according to any one of [1] to [5], wherein m and n represent an integer of 1 to 4.

[7]Such as [1]]～[6]The compound of any one of (A) to (B), wherein (L) is ¹ O) _m Bonded to the carbon atom of substitution position number 2, the above (L) ² O) _n Bonded to the carbon atom at substitution position number 12.

[8]Such as [1]]～[7]Any one of the compounds wherein the carbon atoms at the substitution positions are numbered 1 to 6 and 8 to 13 and are not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

[9] A thermoplastic resin, comprising: a structure in which 2 or more 2-valent structural units are connected via a 2-valent linking group; at least a part of the 2 or more valent-2 structural units is a structural unit represented by the following formula (1); at least a part of the 2-valent linking group is a carbonate bond or an ester bond.

[ solution 5]

In the formula (1), L ¹ And L ² Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

(L ² O) _n bonded to any one of carbon atoms of substitution position numbers 8 to 13;

[10] The thermoplastic resin according to [9], wherein at least a part of the 2 or more 2-valent structural units is a structural unit represented by the formula (1); and at least one or more selected from the group consisting of a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and a structural unit represented by the following formula (8).

[ solution 6]

In the formula (2), R ¹ Represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms and having or not having a substituent;

R ² ～R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

L ³ and L ⁴ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituentAn arylene group having 4 to 10 carbon atoms and having a substituent, or an aralkylene group having 6 to 12 carbon atoms and having or not having a substituent;

o represents an integer of 0 to 4;

p represents an integer of 0 to 4.

[ solution 7]

In the formula (3), R ¹⁰ ～R ²¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

L ⁵ and L ⁶ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may have a substituent, an arylene group having 4 to 10 carbon atoms, which may have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may have a substituent;

q represents an integer of 0 to 4;

r represents an integer of 0 to 4.

[ solution 8]

In the formula (4), V represents an arylene group with or without a substituent;

the substituent for V is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

L ⁷ and L ⁸ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

s represents an integer of 0 to 4;

t represents an integer of 0 to 4.

[ solution 9]

In the formula (5), A ¹ ～A ⁸ Each independently represents ═ CH-or ═ N —;

R ²² 、R ²³ and R ²⁴ Each independently represents a group in which at least 2 groups selected from the group consisting of C1-10 alkylene groups with or without substituents, C4-10 arylene groups with or without substituents, C6-12 aralkylene groups with or without substituents and C1-10 alkylene groups with or without substituents and C4-10 arylene groups with or without substituents are linked by oxygen atoms, C4-10 nitrogen atoms with or without substituents or carbonyl groups;

R ²⁵ ～R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, or a C3 group having an optionally having a substituent14 an aryl group, an acyl group having 1 to 10 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 10 carbon atoms and optionally having a substituent, an aryloxy group having 3 to 14 carbon atoms and optionally having a substituent, an acyloxy group having 1 to 10 carbon atoms and optionally having a substituent, an amino group having or optionally having a substituent, an alkenyl group having 2 to 10 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 10 carbon atoms and optionally having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

R ²⁵ ～R ³² wherein at least 2 adjacent groups may be bonded to each other to form a ring;

v represents an integer of 0 to 5.

[ solution 10]

In the formula (6), K ¹ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

u represents an integer of 0 to 4;

when u is 2 or more, each K ¹ May be the same or different.

[ solution 11]

In the formula (7), K ² Each independently of the otherAnd (b) represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, an aryl group having 3 to 14 carbon atoms and optionally having a substituent, an acyl group having 1 to 10 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 10 carbon atoms and optionally having a substituent, an aryloxy group having 3 to 14 carbon atoms and optionally having a substituent, an acyloxy group having 1 to 10 carbon atoms and optionally having a substituent, an amino group having or optionally having a substituent, an alkenyl group having 2 to 10 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 10 carbon atoms and optionally having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

w represents an integer of 0 to 4;

when w is 2 or more, each K ¹ May be the same or different.

[ solution 12]

In the formula (8), one of the 2 connecting bonds is bonded to any one of the carbon atoms of the substitution position numbers 1-6, and the other connecting bond is bonded to any one of the carbon atoms of the substitution position numbers 8-13;

a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom with a substituent, a halogen atom, a nitro group or a cyano group are independently bonded to the carbon atom not bonded to the above-mentioned connecting bond among the carbon atoms numbered 1 to 6 and 8 to 13 in the substitution position.

[11] The thermoplastic resin according to any one of [9] or [10], wherein either one or both of the above carbonate bond and the above ester bond contain a carbonyl carbon derived from a carbonic acid diester represented by the following formula (°).

[ solution 13]

In the formula (, E) ⁵ And E ⁶ Each independently represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having an optionally having a substituent;

E ⁵ and E ⁶ May be the same or different.

[12] The thermoplastic resin according to any one of [9] to [11], wherein the reduced viscosity is 0.15 to 1.50 dL/g.

[13] The thermoplastic resin according to any one of [9] to [12], wherein the glass transition temperature is 100 to 180 ℃.

[14] The thermoplastic resin according to any one of [9] to [13], wherein the refractive index is 1.62 or more.

[15] An optical member comprising the thermoplastic resin according to any one of [9] to [14 ].

[17] An optical lens comprising the thermoplastic resin according to any one of [9] to [14 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, there can be provided: a compound which, when used as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond, can give a thermoplastic resin having a high refractive index, good moldability, and no risk of mold corrosion; a thermoplastic resin having a high refractive index, good moldability, and no risk of corrosion of a mold; and an optical member and an optical lens comprising the above thermoplastic resin.

Drawings

FIG. 1 is a UV absorption spectrum of 2,12DNF and 2, 12-DODNT.

FIG. 2 shows an extended chain structure of a polycarbonate using 2,12 DNF.

FIG. 3 shows an extended chain structure of a polycarbonate using 3,11 DNF.

FIG. 4 shows an extended chain structure of a polycarbonate using 6,8 DNF.

FIG. 5 is an NMR spectrum of the polycarbonate copolymer of example 1.

FIG. 6 is an NMR spectrum of a polycarbonate copolymer of example 11.

FIG. 7 is an NMR spectrum of a polycarbonate copolymer of example 14.

Detailed Description

The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to the following as long as it does not exceed the gist thereof.

In the present specification, the compound represented by the formula (f) is referred to as "compound (f)", and compounds represented by other formulae are also similarly described.

In the present specification, the structural unit represented by formula (1) is referred to as "structural unit (1)", and structural units represented by other formulae are similarly described.

< Compound >

A compound according to one embodiment of the present disclosure relates to the following compound (f).

[ solution 14]

Wherein, B ¹ And B ² Each independently represents a polymerization reactive group;

L ¹ and L ² Each independently represents an alkylene group having 1 to 10 carbon atoms, which may have a substituent, an arylene group having 4 to 10 carbon atoms, which may have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may have a substituent;

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

(L ¹ O) _m bonded to any one of carbon atoms of substitution position numbers 1-6;

Examples of the optional substituent include: an alkyl group having 1 to 10 carbon atoms, which may or may not have a substituent; an aryl group having 3 to 14 carbon atoms, which may have a substituent; an acyl group having 1 to 10 carbon atoms, which may or may not have a substituent; an alkoxy group having 1 to 10 carbon atoms, which may or may not have a substituent; an aryloxy group having 3 to 14 carbon atoms, which may or may not have a substituent; an acyloxy group having 1 to 10 carbon atoms, which may or may not have a substituent; an amino group with or without a substituent; an alkenyl group having 2 to 10 carbon atoms, which may have a substituent; an alkynyl group having 2 to 10 carbon atoms, which may have a substituent; a silicon atom having a substituent; a halogen atom; a nitro group; a cyano group.

Hereinafter, there will be mentioned unbound (L) groups which may be bound to the carbon atoms of the substitution positions 1 to 6 and 8 to 13 ¹ O) _m Or (L) ² O) _n The atoms or groups on the carbon atoms other than the hydrogen atom in (2) are collectively referred to as "optional substituents".

((L ¹ O) _m 、(L ² O) _n )

L ¹ Or L ² Specific examples of the "alkylene group having 1 to 10 carbon atoms" in the "alkylene group having 1 to 10 carbon atoms which may have a substituent(s)" include, but are not limited to, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, and n-hexyleneLinear alkylene groups such as nonylene and n-decylene; alkylene groups having a branched chain such as 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1-dimethylethylene group, 2-dimethylpropylene group, and 3-methylpropylene group; alkylene containing an alicyclic structure; alkylene groups containing heterocyclic structures. Wherein L is ¹ Or L ² The number of the substitution position in (b) is counted from the carbon on the dinaphthofuran side.

In the alkylene group containing an alicyclic structure, examples of the alicyclic structure include those shown in the following group [ E ].

Examples of the alkylene group containing an alicyclic structure include a group composed of an alicyclic structure and 2 linear or branched alkylene groups bonded to any 2 positions of the alicyclic structure. This group can also be said to be a group in which an alicyclic structure is interposed between 2 linear or branched alkylene groups. The bonding position of 2 alkylene groups in the alicyclic structure is arbitrary, and 2 alkylene groups may be bonded to the same carbon atom.

[ chemical 15]

In the alkylene group having a heterocyclic structure, examples of the heterocyclic structure include those shown in the following group [ F ].

Examples of the alkylene group having a heterocyclic structure include a group composed of a heterocyclic structure and 2 linear or branched alkylene groups bonded to arbitrary 2 positions of the heterocyclic structure. This group can also be said to be a group having a heterocyclic structure between 2 linear or branched alkylene groups. The bonding positions of 2 alkylene groups in the heterocyclic structure are arbitrary, and 2 connecting bonds may be substituted on the same carbon atom.

[ chemical 16]

Specific examples of the linear or branched alkylene group bonded to the alicyclic structure or heterocyclic structure include, but are not limited to, linear alkylene groups such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene; 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1-dimethylethylene group, 2-dimethylpropylene group, 3-methylpropylene group and the like contain a branched alkylene group (wherein the number of substitution positions herein is counted from the carbon bonded to the above-mentioned ring structure).

Examples of the substituent which the alkylene group having 1 to 10 carbon atoms may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; and an aryl group having 4 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.) having 1 to 3 substituents selected from a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, isopropyl group), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group), an acyl group having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group), an acylamino group having 1 to 10 carbon atoms (e.g., acetylamino group, benzoylamino group), a nitro group, a cyano group, etc. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the C1-10 alkylene group which may have a substituent include phenylmethylene, 1-phenylethylene, 1-phenylpropylene, 1-cyclohexylpropylene and 1,1,2, 2-tetrafluoroethylene.

L ¹ Or L ² Wherein the "carbon" in the "arylene group having 4 to 10 carbon atoms with or without substituent(s)"Specific examples of the arylene group having 4 to 10 atoms "include, but are not limited to, phenylene groups such as 1, 2-phenylene, 1, 3-phenylene, and 1, 4-phenylene; naphthylene groups such as 1, 5-naphthylene group and 2, 6-naphthylene group; heteroarylene groups such as 2, 5-pyridylene and 2, 4-furanylene.

Examples of the substituent which the arylene group having 4 to 10 carbon atoms may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; and an aryl group having 4 to 10 carbon atoms (e.g., phenyl group, naphthyl group) having 1 to 3 substituents selected from a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, isopropyl group), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group), an acyl group having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group), an acylamino group having 1 to 10 carbon atoms (e.g., acetylamino group, benzamido group), a nitro group, a cyano group, and the like. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the arylene group having 4 to 10 carbon atoms which may have a substituent include 2-methyl-1, 4-phenylene, 3, 5-dimethyl-1, 4-phenylene, 3-methoxy-1, 4-phenylene, 3-trifluoromethyl-1, 4-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2,3,5, 6-tetrafluoro-1, 4-phenylene, 2,3,5, 6-tetrachloro-1, 4-phenylene, 3-nitro-1, 4-phenylene, and 3-cyano-1, 4-phenylene.

L ¹ Or L ² In the above formula, "aralkylene group having 6 to 12 carbon atoms" in "aralkylene group having 6 to 12 carbon atoms which may have a substituent" includes, for example, a group composed of an aromatic ring structure and 2 linear or branched alkylene groups bonded to arbitrary 2 positions of the aromatic ring structure. Fragrance compositionThe ring structure may be a hydrocarbon ring structure such as a benzene ring or a naphthalene ring, or a heterocyclic ring structure such as a furan ring or a pyridine ring.

Specific examples of the aralkylene group having 6 to 12 carbon atoms include, but are not limited to, those shown in the following group [ G ].

[ solution 17]

Examples of the substituent which the above-mentioned aralkylene group having 6 to 12 carbon atoms may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; and a C4-10 aryl group (e.g., phenyl, naphthyl, etc.) having 1-3 substituents selected from a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an alkyl group having 1-10 carbon atoms (e.g., methyl, ethyl, isopropyl), an alkoxy group having 1-10 carbon atoms (e.g., methoxy, ethoxy), an acyl group having 1-10 carbon atoms (e.g., acetyl, benzoyl), an acylamino group having 1-10 carbon atoms (e.g., acetylamino, benzoylamino), a nitro, a cyano, etc. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the C6-10 aralkylene group which may have a substituent include 2-methyl-1, 4-xylylene group, 2, 5-dimethyl-1, 4-xylylene group, 2-methoxy-1, 4-xylylene group, 2, 5-dimethoxy-1, 4-xylylene group, 2,3,5, 6-tetrafluoro-1, 4-xylylene group, α, α -dimethyl-1, 4-xylylene group, and α, α, α ', α' -tetramethyl-1, 4-xylylene group.

L is low-cost raw material supply and easy synthesis ¹ And L ² Each of the alkylene groups is preferably an alkylene group having 1 to 10 carbon atoms, which may have a substituent, and more preferably a linear alkylene group or an alkylene group having an alicyclic structure. Further preferred are methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, 2-dimethylpropylene, and the following [ H]Alkylene groups shown in group (a) containing an alicyclic structure.

[ solution 18]

Wherein the substitution position of 2 methylene groups in each alicyclic structure shown in the above group [ H ] is arbitrary, and 2 methylene groups may be bonded to the same carbon atom.

Among the above groups, preferred are methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene and 2, 2-dimethylpropylene.

Since the glass transition temperature tends to decrease as the chain length increases, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene are more preferable from the viewpoint of moldability.

When the molecular structure is small, the concentration of the dinaphthofuran structure in the unit structure can be increased, and therefore, from the viewpoint of high refractive index, n-butylene, n-propylene, ethylene, and methylene are more preferable. When the polymerizable reactive group is a hydroxyl group-containing group, an ethylene group is particularly preferable in order to achieve an excellent balance between optical properties and mechanical strength and an excellent thermal stability. On the other hand, when the polymerizable reactive group is an ester group, a carboxyl group, an acid halide group, or a hydroxy ester group, a methylene group or an ethylene group is particularly preferable in order to obtain an excellent balance between the optical characteristics and the mechanical strength. Methylene and ethylene also have the advantage of being able to be introduced in a short time and at a low cost industrially.

L ¹ Or L ² When the group is an alkylene group having 2 to 10 carbon atoms, which may have a substituent, L bonded to a polymerizable group, particularly a hydroxyl group is preferable ¹ Or L ² The carbon atom at the beta position of (2) is not bonded with a hydrogen atom. When no hydrogen atom is bonded to the carbon atom at the β -position, no olefin is produced by proton dissociation during polymerization, and therefore, the heat resistance is high and the thermal stability is excellent.

Examples of the alkylene group having no hydrogen atom bonded to the β -position carbon atom of the hydroxyl group include groups in which all of the hydrogen atoms of the β -position carbon atom of a linear alkylene group such as 2, 2-dimethylpropylene group are substituted with an alkyl group.

m and n each represent an integer of 0 to 4. In a preferred embodiment, m and n each represent an integer of 1 to 4.

When m is 0, B ¹ Directly bonded to any one of the carbon atoms in the substitution position numbers 1 to 6. When m is an integer of 1 to 4, B ¹ Via (L) ¹ O) _m Bonded to any one of the carbon atoms of substitution position numbers 1-6.

When n is 0, B ² Directly bonded to any one of the carbon atoms of substitution positions No. 8 to No. 13. When n is an integer of 1 to 4, B ² Via (L) ² O) _n Bonded to any one of the carbon atoms of substitution position numbers 8 to 13.

(L ¹ O) _m Or (L) ² O) _n The longer the chain length of (b) is, the lower the glass transition temperature of the resulting thermoplastic resin tends to be, and the higher the fluidity tends to be, and therefore m and n are each preferably 3 or 4 from the viewpoint of moldability.

On the other hand, (L) ¹ O) _m Or (L) ² O) _n The longer the chain length of (b) is, the more the refractive index of the resulting thermoplastic resin tends to decrease, and therefore m and n are preferably 1 or 2, respectively. In view of excellent balance between optical characteristics and mechanical strength, m and n are each particularly preferably 1.

m and n may be the same value or different values. In view of the asymmetric skeleton, which lowers the glass transition temperature of the thermoplastic resin and further improves the moldability, it is preferable that m and n have different values.

m or m is an integer of 2 to 4, m L ¹ Or n of L ² May be the same or different.

In a preferred embodiment, (L) ¹ O) _m Bonded to the carbon atom of substitution position number 2, (L) ² O) _n Bonded to the carbon atom at substitution position number 12. In this case, the refractive index of the obtained thermoplastic resin is further increased.

In another preferred embodiment, (L) ¹ O) _m Bonded to the carbon atom of substitution position No. 3, (L) ² O) _n Bonded to the carbon atom of substitution position number 11. In this case, the refractive index of the obtained thermoplastic resin is further increased. In addition, the glass transition temperature of the thermoplastic resin is increased, and the heat resistance is improved.

(optional substituents)

Specific examples of the "alkyl group having 1 to 10 carbon atoms" in the "alkyl group having 1 to 10 carbon atoms which may have a substituent(s)" among the optional substituents include, but are not limited to, linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-decyl group; branched alkyl groups such as isopropyl group, 2-methylpropyl group, 2-dimethylpropyl group, and 2-ethylhexyl group; and cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl.

Examples of the substituent which the alkyl group having 1 to 10 carbon atoms may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; and an aryl group having 3 to 14 carbon atoms (e.g., phenyl group, naphthyl group) having 1 to 3 substituents selected from a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, isopropyl group), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group), an acyl group having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group), an acylamino group having 1 to 10 carbon atoms (e.g., acetylamino group, benzamido group), a nitro group, a cyano group, and the like. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent include a trifluoromethyl group, a benzyl group, a 4-methoxybenzyl group and a methoxymethyl group.

Specific examples of the "aryl group having 3 to 14 carbon atoms" in the "aryl group having 3 to 14 carbon atoms with or without a substituent" among the optional substituents include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, 1-imidazolyl, 2-pyridyl, 2-furyl, and 9-carbazolyl.

Examples of the substituent which the aryl group having 3 to 14 carbon atoms may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; an aryl group having 3 to 14 carbon atoms (e.g., phenyl group, naphthyl group, etc.) which may have 1 to 3 substituents selected from a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, isopropyl group), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group), an acyl group having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group), an acylamino group having 1 to 10 carbon atoms (e.g., acetylamino group, benzoylamino group), a nitro group, a cyano group, etc.; and so on. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the aryl group having 3 to 14 carbon atoms which may have a substituent include a 2-methylphenyl group, a 4-methylphenyl group, a 3, 5-dimethylphenyl group, a 4-benzoylphenyl group, a 4-methoxyphenyl group, a 4-nitrophenyl group, a 4-cyanophenyl group, a 3-trifluoromethylphenyl group, a 3, 4-dimethoxyphenyl group, a 3, 4-methylenedioxyphenyl group, a 2,3,4,5, 6-pentafluorophenyl group and a 4-methylfuranyl group.

Specific examples of the "acyl group having 1 to 10 carbon atoms" in the "acyl group having 1 to 10 carbon atoms which may have a substituent(s)" among the optional substituents include, but are not limited to, aliphatic acyl groups such as formyl group, acetyl group, propionyl group, 2-methylpropanoyl group, 2-dimethylpropanoyl group, and 2-ethylhexanoyl group; aromatic acyl groups such as benzoyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl and 2-furylcarbonyl.

Examples of the substituent that the acyl group having 1 to 10 carbon atoms may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl); an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group or a benzoyl group); an acylamino group having 1 to 10 carbon atoms (e.g., an acetylamino group, a benzoylamino group); a nitro group; a cyano group; an aryl group having 3 to 14 carbon atoms (e.g., phenyl group, naphthyl group) which may have 1 to 3 substituents selected from a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, isopropyl group), an alkoxy group having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group), an acyl group having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group), an acylamino group having 1 to 10 carbon atoms (e.g., acetylamino group, benzoylamino group), a nitro group, a cyano group, etc.; and so on. The number of the substituent is not particularly limited, but is preferably 1 to 3. When the number of the substituents is 2 or more, the substituents may be the same or different.

Specific examples of the acyl group having 1 to 10 carbon atoms which may have a substituent include a chloroacetyl group, a trifluoroacetyl group, a methoxyacetyl group, a phenoxyacetyl group, a 4-methoxybenzoyl group, a 4-nitrobenzoyl group, a 4-cyanobenzoyl group and a 4-trifluoromethylbenzoyl group.

Specific examples of the "alkoxy group having 1 to 10 carbon atoms which may have a substituent" among the optional substituents include, but are not limited to, methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, and trifluoromethoxy group.

Specific examples of the "aryloxy group having 3 to 14 carbon atoms which may have a substituent" in an arbitrary substituent include, but are not limited to, phenoxy.

Specific examples of the "acyloxy group having 1 to 10 carbon atoms which may have a substituent" among the optional substituents include, but are not limited to, acetoxy and benzoyloxy.

Specific examples of the "alkenyl group having 2 to 10 carbon atoms which may have a substituent" among the optional substituents include, but are not limited to, vinyl groups.

Specific examples of "alkynyl having 2 to 10 carbon atoms with or without a substituent" among the optional substituents include, but are not limited to, ethynyl.

Specific examples of the "halogen atom" in an arbitrary substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The optional substituent is preferably a phenyl group, a naphthyl group, an acyl group, a 9-carbazolyl group, a halogen atom, a nitro group or a cyano group from the viewpoint of a high refractive index, more preferably a phenyl group, a naphthyl group, a bromine atom or a cyano group from the viewpoint of a high refractive index and low cost synthesis, and particularly preferably a phenyl group or a naphthyl group from the viewpoint of coloring and thermal stability.

When the compound (f) has 2 or more optional substituents, the optional substituents may be the same or different in kind, and are preferably the same from the viewpoint of low-cost synthesis.

The number of optional substituents of the compound (f) is not particularly limited, but is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less, from the viewpoint of ease of synthesis.

The compound (f) has an optional substituent from the viewpoint of being industrially producible at low costThe number of generation groups is preferably 0. That is, it is preferable that the carbon atoms at the substitution positions are not bonded (L) in the carbon atoms of 1 to 6 and 8 to 13 ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

(polymerization reactive group)

B ¹ And B ² Examples of the polymerization reactive group include a group having a hydroxyl group (hereinafter also referred to as a "hydroxyl group-containing group"), an ester group having a hydroxyl group (hereinafter also referred to as a "hydroxyl ester group"), a group having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing group"), and a group having an acid halide (hereinafter also referred to as an "acid halide-containing group"). The compound (f) having such a polymerization reactive group can be used as a monomer of a thermoplastic resin (polyester, polycarbonate, polyestercarbonate, or the like) having either or both of a carbonate bond and a polyester bond.

Specific examples of the hydroxyl group-containing group include, but are not limited to, hydroxyl group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxybutyl group, 2-dimethyl-3-hydroxypropyl group, 2-methoxymethyl-2-methylpropylidene group, 4-hydroxyphenyl group, 4-hydroxy-3-methylphenyl group, 4- (2-hydroxyethoxy) phenyl group, and (4- (hydroxymethyl) cyclohexan-1-yl) methyl group.

Specific examples of the ester group include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl and 2- (methoxycarbonyl) propyl.

Specific examples of the hydroxy ester group include, but are not limited to, 2-hydroxyethoxycarbonyl, 3-hydroxy-2, 2-dimethylpropyleneoxycarbonyl, 2- (2-hydroxyethoxy) carbonylethyl, 2- (2-hydroxyethoxy) carbonylpropyl, 2- (4-hydroxybutoxy) carbonylethyl, and 2- [ [4- (hydroxymethyl) cyclohexan-1-yl ] methoxy ] carbonylethyl.

Specific examples of the carboxyl group-containing group include, but are not limited to, a carboxyl group, a carboxymethyl group, and a carboxyethyl group.

Specific examples of the acid halide-containing group include, but are not limited to, acid chlorides, acid bromides, carbonylmethyl chlorides and carbonylmethyl bromides.

As the polymerization reactive group, a hydroxyl group-containing group, an ester group, a carboxyl group-containing group, or a hydroxyl ester group is preferable for reasons of usefulness as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond.

The hydroxyl group is more preferable for the reason that it can be widely used in thermoplastic resins such as polycarbonate, polyester, and polyester carbonate.

The hydroxy ester group is more preferable in terms of imparting appropriate flexibility and fluidity to a thermoplastic resin having either or both of a carbonate bond and a polyester bond. 2-hydroxyethoxycarbonyl is more preferable because it can be produced industrially at low cost. From the viewpoint of polymerization reactivity in the production of a thermoplastic resin such as a polyester or a polyester carbonate, a phenoxycarbonyl group is more preferable.

In view of good polymerization reactivity and the ability to obtain a thermoplastic resin by relatively simple equipment such as solution polymerization and interfacial polymerization, an acid chloride-containing group is preferable, and an acid chloride or an acid bromide that can be industrially produced at low cost is more preferable.

B ¹ And B ² May be the same or different. In different cases, as B ¹ And B ² Combinations of (a) and (b) include, for example, hydroxymethyl and ethoxycarbonyl; 2- (2-hydroxyethoxy) carbonyl and carboxyl; 2- (2-hydroxyethoxy) carbonylethyl and carboxyethyl; and the like.

For the reason that the compound (f) tends to be produced in a short process, B is preferred ¹ And B ² The same is true.

The compound (f) can be used as a monomer for various thermoplastic resins, but the polymerization reactive group is preferably only B ¹ And B ² At this point 2. That is, the substituent which functions as a polymerization reactive group under polymerization conditions for producing various thermoplastic resins is preferably not bonded (L) ¹ O) _m Or (L) ² O) _n The number of the substitution positions 1 to 6 and 8 to 13 does not exist.

In the preferred aspectsIn one embodiment, B in the formula (f) ¹ And B ² Is a hydroxyl group. B is ¹ And B ² The compound (f) which is a hydroxyl group is the following compound (f 1). The compound (f1) is a monomer (an example of a dihydroxy compound) which is excellent in optical properties and can be used in general for polyesters, polycarbonates and polyester carbonates which are preferable thermoplastic resins.

[ solution 19]

Wherein L is ¹ And L ² Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

non-bonded (L) in carbon atoms of substitution positions 1 to 6,8 to 13 ¹ O) _m Or (L) ² O) _n The carbon atom of (A) is independently bonded with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and having or not having a substituent, an aryl group having 3 to 14 carbon atoms and having or not having a substituent, an acyl group having 1 to 10 carbon atoms and having or not having a substituent, an alkoxy group having 1 to 10 carbon atoms and having or not having a substituent, an aryloxy group having 3 to 14 carbon atoms and having or not having a substituent, an acyloxy group having 1 to 10 carbon atoms and having or not having a substituent, an amino group having or not having a substituent, an alkenyl group having 2 to 10 carbon atoms and having or not having a substituent, an alkynyl group having 2 to 10 carbon atoms and having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group.

In the formula (f1), L ¹ 、L ² Specific examples and preferred modes of m, n and optional substituents are the same as those described above.

In the formula (f1), the carbon atoms in the substitution positions 1 to 6 and 8 to 13 are preferably not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

In another preferred embodiment, B in formula (f) ¹ And B ² Is an ester group. B is ¹ And B ² The ester-based compound (f) is a monomer (diester compound) which can be used in general for polyesters and polyester carbonates as preferred thermoplastic resins because of its excellent optical properties.

The ester group is preferably a 2- (methoxycarbonyl) ethyl group, a 2- (ethoxycarbonyl) ethyl group or a 2- (methoxycarbonyl) propyl group, because methyl acrylate, ethyl acrylate or methyl methacrylate which is industrially available can be easily introduced.

The ester group is preferably a phenoxycarbonylalkyl group because the diester compound, dihydroxy compound and carbonic acid diester can be reacted under the same conditions to synthesize a polyester carbonate as a preferable thermoplastic resin in one step because the activity of the ester group is increased and the ester exchange reaction is easily progressed. In particular, 2- (phenoxycarbonyl) methyl, 2- (phenoxycarbonyl) ethyl, and 2- (phenoxycarbonyl) propyl can be introduced by using 2-bromophenyl acetate, phenyl acrylate, and phenyl methacrylate; introduction methods based on transesterification starting from 2-bromoacetate, 2-chloroacetate, 2-iodoacetate, acrylates, methacrylates are particularly preferred.

B ¹ And B ² The compound (f) which is an ester group is, for example, the following compound (f 2).

[ solution 20]

Wherein, B ³ And B ⁴ Each independently represents a hydroxyl group, an organic substituent having 1 to 10 carbon atoms or a halogen atom,

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

In the formula (f2), L ¹ 、L ² Specific examples and preferred modes of m, n and optional substituents are the same as those described above.

In the formula (f2), the carbon atoms in the substitution positions 1 to 6 and 8 to 13 are preferably not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

B ³ And B ⁴ Specific examples of the organic substituent having 1 to 10 carbon atoms includeBut are not limited to, linear alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, and n-decoxy; branched alkoxy groups such as isopropoxy, 2-methylpropoxy, 2-dimethylpropoxy, and 2-ethylhexyloxy; cyclic alkoxy groups such as cyclopropyloxy, cyclopentyloxy, cyclohexyloxy and cyclooctyloxy; aryloxy groups such as phenoxy, 1-naphthyloxy, 2-pyridyloxy, and 2-furyloxy; aralkyloxy groups such as benzyloxy, 2-phenylethoxy, and p-methoxybenzyloxy.

Specific examples of the halogen atom include, but are not limited to, a chlorine atom and a bromine atom.

B is effective for the synthesis of polyesters and polyester carbonates by removing low-boiling alcohols generated during the transesterification with dihydroxy compounds ³ And B ⁴ Preferably methoxy or ethoxy.

B is because the diester compound, dihydroxy compound and carbonic acid diester are added to the reactor at one time for the reason that the ester interchange reaction is easy to proceed, and thereby a polyester carbonate as a preferable polymer can be synthesized in one step ³ And B ⁴ Preferably an aryloxy group. Particularly preferred are phenoxy groups which have a low molecular weight and can be distilled off as phenol after the synthesis of the polyester carbonates.

B is used in the method for producing a thermoplastic resin described later ³ And B ⁴ In the case of the aryloxy compound, the diaryl carbonates described later are preferably used as the carbonic acid diester from the viewpoint of reactivity at the time of polymerization, and B is more preferably used from the viewpoint of easy removal of by-products ³ And B ⁴ The aryloxy group of (b) is the same as the aryloxy group in the diaryl carbonate group.

In another preferred embodiment, B in formula (f) ¹ And B ² Is a hydroxy ester group. B is ¹ And B ² The compound (f) which is a hydroxy ester group is a monomer which can be used in general in polyesters and polyester carbonates which are preferable thermoplastic resins because of its excellent optical properties.

B ¹ And B ² The compound (f) which is a hydroxy ester group is, for example, the compound (f3) described below.

[ solution 21]

Wherein, B ⁵ 、B ⁶ 、L ¹ And L ² Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

In the formula (f3), L ¹ 、L ² Specific examples and preferred modes of m, n, and optional substituents are the same as those described above.

B ⁵ And B ⁶ Chinese "An alkylene group having 1 to 10 carbon atoms which may have a substituent, an arylene group having 4 to 10 carbon atoms which may have a substituent, an aralkylene group having 6 to 12 carbon atoms which may have a substituent, and L ¹ And L ² Are the same as those in (1).

In the formula (f3), the carbon atoms in the substitution positions 1 to 6 and 8 to 13 are preferably not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

(specific examples of Compound (f))

Specific examples of the compound (f) include the compounds shown in the following groups [ I-1] to [ I-5 ]. [ I-1] to [ I-5] wherein Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Cl represents a chlorine group, and Br represents a bromine group.

[ solution 22]

[ solution 23]

[ solution 24]

[ solution 25]

[ solution 26]

Among the compounds represented by the above groups [ I-1] to [ I-4], the compounds having no hydrogen atom bonded to the carbon atom at the position β to the hydroxyl group are preferable because they do not generate olefin due to proton dissociation during polymerization, and therefore, they have high heat resistance. Among them, from the viewpoint of low-cost raw material supply, a compound of the following structural formula group in which 2 methyl groups are bonded to the carbon atom β to the hydroxyl group is also preferable.

[ solution 27]

From the viewpoint of high refractive index and low cost of raw material supply, compounds of the following structural formula group are preferred.

[ solution 28]

The compounds of the following structural formula group are most preferable from the viewpoints of high refractive index, low-cost raw material supply, and low birefringence.

[ solution 29]

(method for producing Compound (f))

The method for producing the compound (f) is not limited at all. For example, a polymerizable reactive group (B) ¹ 、B ² ) An example of the compound (f1) having a hydroxyl group can be produced by production method a shown by the following formula.

[ solution 30]

In production method a, compound (D2) is obtained by directly bonding compound (D1a) and compound (D1 b). Followed by introducing a modifying group P into one of the 2 hydroxyl groups of the above-mentioned compound (D2) ¹ To obtainCompound (D3). Then, the compound (D3) is dehydrated and ring-closed to obtain a compound (D4). Followed by reacting the modifying group P of the compound (D4) ¹ To obtain compound (D5). And compound (f1) is obtained by elongation of the hydroxyl group of compound (D5).

The compound (D1a) and the compound (D1b) are each a dihydroxynaphthalene having or not having a substituent, and one of the 2 hydroxyl groups is bonded to the 2-position carbon atom of the naphthalene ring, and the other is bonded to any one of the 3-position to 8-position carbon atoms. A hydrogen atom or an optional substituent (an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom with a substituent, a halogen atom, a nitro group or a cyano group) is independently bonded to a carbon atom to which a hydroxyl group is not bonded among carbon atoms at positions 3 to 8 of the naphthalene ring. A hydrogen atom is bonded to the carbon atom at the 1-position of the naphthalene ring.

The compound (D1a) may be the same as or different from the compound (D1 b).

As a method for directly bonding the compound (D1a) and the compound (D1b), for example, a method in which the compound (D1a) and the compound (D1b) are reacted (oxidative coupling) in the presence of an oxidizing agent can be mentioned.

Examples of the oxidizing agent include iron (III) chloride, copper (II) sulfate, potassium persulfate, copper (II) acetylacetonate, copper (II) chloride, hydrogen peroxide, and di-t-butyl peroxide.

The amount of the oxidizing agent used is, for example, 0.1 to 5.0 moles per 1 mole of the total of the compound (D1a) and the compound (D1 b). The reaction temperature is, for example, 0 to 120 ℃. The reaction time is, for example, 0.5 to 12 hours. The reaction may be carried out in the presence of a solvent such as water or isopropyl alcohol.

After the reaction, the reaction product is purified as necessary. As a purification method, various purification methods such as extraction, concentration, column chromatography, filtration, washing and the like can be suitably employed.

Modifying group P ¹ There is no particular limitation as long as it functions as a protecting group for a hydroxyl group. Examples thereof include methyl, acetyl, benzyl, pivaloyl and p-toluenesulfonyl.

The compound (D2) has a modifying group P introduced into one of 2 hydroxyl groups, specifically, a hydroxyl group bonded to a carbon atom at the 3-to 8-positions of the naphthalene ring ¹ E.g. in the modification of the group P ¹ In the case of a methyl group, a method of reacting compound (D2) with methanol in the presence of sulfuric acid is exemplified.

The amount of the sulfuric acid to be used is, for example, 0.001 to 5.0 mol based on 1mol of the compound (D2). The reaction temperature is, for example, 0 to 150 ℃. The reaction time is, for example, 1 to 200 hours.

After the reaction, the reaction product is purified as necessary.

As a method for dehydrating and ring-closing the compound (D3), for example, a method in which the compound (D3) is heated in an organic solvent in the presence of p-toluenesulfonic acid is mentioned.

Examples of the organic solvent include toluene, xylene, trimethylbenzene, chlorobenzene, tetralin, and o-dichlorobenzene.

The amount of p-toluenesulfonic acid used is, for example, 0.01 to 5mol based on 1mol of compound (D3). The heating temperature is, for example, 0 to 200 ℃. The heating time is, for example, 1 to 200 hours.

After the reaction, the reaction product is purified as necessary.

As a modifying group P for Compound (D4) ¹ Method of detachment according to the modifying group P ¹ The kind of (b) may be changed, and various deprotection methods can be suitably employed.

For example a modifying group P ¹ In the case of a methyl group, it can be removed by a strong acid such as boron tribromide. The reaction temperature in this case is, for example, -100 to 100 ℃. The reaction time is 1E to EFor 100 hours.

After the reaction, the reaction product is purified as necessary.

Examples of a method for extending the hydroxyl group of the compound (D5) include a method in which the compound (D5) is reacted with an alkylene carbonate (e.g., ethylene carbonate) in the presence of potassium carbonate. In this case, L is obtained ¹ And L ² A compound which is an alkylene group (f 1).

The amount of potassium carbonate used is, for example, 0.01 to 5.0 moles based on 1 mole of compound (D5). The reaction temperature is, for example, 0 to 180 ℃. The reaction time is, for example, 0.5 to 200 hours. The reaction may be carried out in the presence of a solvent such as dimethylformamide.

After the reaction, the reaction product is purified as necessary.

L ¹ And L ² The compound (f1) which is an arylene group is obtained, for example, by reacting a hydroxyl group bonded to a carbon atom at the 3-to 8-positions of the naphthalene ring of the compound (D2) with dihydroxybenzene in the presence of an acid, followed by ring closure.

L ¹ And L ² The compound (f1) which is an aralkylene group can be obtained, for example, by using (bromomethyl) benzyl alcohol and a base in the elongation of the hydroxyl group of the compound (D5).

By using alkyl bromoacetate, alkyl chloroacetate and a base for elongation of the hydroxyl group of the compound (D5), the polymerizable reactive group (B) can be obtained ¹ 、B ² ) An example of the ester-based compound (f2) is shown below.

An example of the compound (f2) can also be obtained by directly bonding the following compounds (D1a '), (D1 b') instead of the compounds (D1a) and (D1b) and then performing the same step as in the synthesis of the compound (D5).

Further, the polymerizable reactive group (B) can be obtained by condensing the ester group of the compound (f2) with ethylene glycol or the like ¹ 、B ² ) An example of the compound (f3) is a hydroxy ester group.

[ solution 31]

(Effect of Compound (f))

When the compound (f) is used as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond, a thermoplastic resin having a high refractive index, good moldability, and no risk of mold corrosion can be obtained.

When the monomer having a dinaphthothiophene skeleton used in patent document 2 is used, the refractive index is 1.655 and the glass transition temperature is 144 ℃, and the refractive index is increased while maintaining the glass transition temperature which is considered to be good in moldability. The reason why the dinaphthothiophene skeleton has a high refractive index is considered to be that the dinaphthothiophene skeleton contains a sulfur atom having a high polarizability and has a condensed and extended conjugated structure. The reason why the glass transition temperature is low despite having an extended conjugated structure is considered to be that thiophene and naphthalene rings are not on the same plane due to steric hindrance of the naphthalene rings, and therefore interaction between aromatic rings in the resin is hindered. However, according to the studies of the present inventors, it has been found that sulfur dioxide is generated in a resin having a dinaphthothiophene skeleton at around the molding temperature. The sulfur dioxide is presumed to be derived from a sulfur atom contained in a dinaphthothiophene skeleton.

The present inventors have conducted intensive studies and, as a result, have found that a high refractive index and molding processability can be both achieved by introducing a dinaphtho [2,1-b:1 ', 2' -d ] furan represented by the following formula (hereinafter, simply referred to as "dinaphthofuran" for convenience) skeleton into a resin. Here, the numbers in the formulae are substitution position numbers.

[ chemical No. 32]

As described above, the inclusion of a sulfur atom having a high polarizability is considered to be the cause of the high refractive index of the dinaphthothiophene skeleton, but surprisingly, in the dinaphthofuran skeleton, although the sulfur atom becomes an oxygen atom having a lower polarizability than that, the dinaphthothiophene skeleton likewise exhibits a very high refractive index.

In the dinaphthothiophene skeleton, the thiophene ring and the naphthalene ring are significantly deformed because the sulfur atom in the skeleton is large. On the other hand, the dinaphthofuran skeleton contains an oxygen atom having a smaller atomic size in place of a sulfur atom. Therefore, it is considered that the dinaphthofuran skeleton has a conjugated structure more extended than dinaphthothiophene by suppressing the deformation of the furan ring and the naphthalene ring, thereby causing the dinaphthofuran skeleton to exhibit a high refractive index as high as that of the dinaphthothiophene skeleton.

As a result of the studies conducted by the present inventors, it was found that the absorption coefficient on the long wavelength side of the dinaphthofuran skeleton is increased as compared with the dinaphthothiophene skeleton. This supports the above study (see fig. 1).

Further, although it is considered that deformation of the dinaphthofuran skeleton is suppressed as compared with the dinaphthothiophene skeleton, the resin containing the dinaphthofuran skeleton exhibits a low glass transition temperature and exhibits good moldability. This is considered to be due to the fact that (L) is bonded to the dinaphthofuran skeleton ¹ O) _m Or (L) ² O) _n The result is that.

< thermoplastic resin >

A thermoplastic resin according to one embodiment of the present disclosure includes: a structure in which 2 or more 2-valent structural units (hereinafter also simply referred to as "structural units") are linked via a 2-valent linking group (hereinafter also simply referred to as "linking group"). The terminal unit of 2 or more structural units may be bonded with a linking group or a polymerization reactive group.

At least a part of the 2 or more structural units is a structural unit (1).

From the viewpoint of achieving a balance between the refractive index and the glass transition temperature and facilitating both of the high refractive index and the moldability, the 2 or more structural units preferably include the structural unit (1) and at least one selected from the group consisting of the structural units (2) to (8).

In a preferred embodiment, at least a part of the 2-valent structural units of 2 or more are structural units (1); and at least one or more selected from the group consisting of a structural unit (2), a structural unit (3), a structural unit (4), a structural unit (5), a structural unit (6), a structural unit (7), and a structural unit (8).

The 2 or more structural units may further contain structural units other than the structural units (1) to (8) to the extent that the characteristics of the present invention are not impaired.

The structural units (1) to (8) and other structural units are described in detail below.

At least a portion of the linking group is a carbonate linkage (-O-C (-O) -O-) or an ester linkage (-O-C (-O) -).

In the case where 2 or more linking groups are present in the thermoplastic resin, a linking group as a carbonate bond and a linking group as an ester bond may coexist. Part of the linking group may be a carbonate bond or a bond other than an ester bond. Examples of the other bond include an amide bond, a phosphonate bond, and a sulfone bond.

In view of being able to synthesize the thermoplastic resin at low cost and easily, it is preferable that all the linking groups in the thermoplastic resin are carbonate bonds or ester bonds. In view of excellent hydrolysis resistance, a carbonate bond is more preferable, and the entire linking groups in the thermoplastic resin are particularly preferably carbonate bonds.

When the linking group is asymmetric as in the case of an ester bond, the linking group can link 2 adjacent structural units in an arbitrary direction.

As an example of the thermoplastic resin, a thermoplastic resin having a repeating unit represented by the following formula (X) can be given.

[ solution 33]

Wherein Q ¹ Represents a structural unit based on a dihydroxy compound, Q ² Represents a structural unit based on a dicarboxylic acid compound, and a represents 0 or 1.

The "structural unit based on a dihydroxy compound" is a moiety obtained by removing 2 hydroxyl groups from a dihydroxy compound having 2 hydroxyl groups.

The "structural unit based on a dicarboxylic acid compound" is a moiety obtained by removing 2 functional groups from a dicarboxylic acid compound having 2 carboxyl groups or an ester-forming derivative (ester, etc.) thereof. The 2 functional groups of the dicarboxylic acid compound are typically represented by-C (═ O) -X ¹ As indicated. Here, X ¹ Represents OH, OX ² Or a halogen atom; x ² Represents an organic substituent having 1 to 10 carbon atoms.

Examples of the thermoplastic resin having a repeating unit represented by the formula (X) include polycarbonates, polyesters, and polyester carbonates. In the case of polycarbonate, a is 0. In the case of the polyester, a is 1. In the case of polyester carbonates, these have a repeating unit with a being 0 and a repeating unit with a being 1.

In the thermoplastic resin having the repeating unit represented by the formula (X), at least a part of the repeating unit represented by the formula (X) is Q ¹ And Q ² At least one of which is a repeating unit of the structural unit (1).

When the thermoplastic resin is a polycarbonate, polyester or polyestercarbonate obtained using a dihydroxy compound at least a part of which is the compound (f1), Q is contained in at least a part of the repeating units represented by the formula (X) ¹ Is a structural unit (1). In this case, when a in the formula (X) is 1, Q is ² Any one of the structural units (1) to (8) may be used, or another structural unit may be used.

When the thermoplastic resin is a polyester or a polyester carbonate obtained using a dicarboxylic acid compound at least a part of which is the compound (f2) or the compound (f3), Q in at least a part of the repeating units represented by the formula (X) ² Is a structural unit (1). In this case, Q ¹ Any one of the structural units (1) to (8) may be used, or another structural unit may be used.

In this way, in the thermoplastic resin of the present disclosure, the structural unit based on the compound (f) may be constituted as Q ¹ (structural unit based on dihydroxy Compound) or may be Q ² (structural units based on dicarboxylic acid compounds).

Q in the formula (X) among thermoplastic resins ¹ A and Q ² Any one or more of them may have two or more kinds of repeating units different from each other.

(structural Unit (1))

The structural unit (1) is represented by the following formula (1).

[ chemical 34]

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

In the formula (1), L ¹ 、L ² Specific examples and preferred modes of m, n and optional substituents are the same as those of the compound (f).

Specific examples of the structural unit (1) include the structural units shown in the following groups [ J-1] to [ J-3 ].

[ solution 35]

[ solution 36]

[ solution 37]

Among the above-mentioned structural units, those shown in the following group [ K ] are preferable in view of the balance between ease of synthesis and high refractive index.

[ solution 38]

Among the above-mentioned structural units, the structural units shown in the following group [ M ] are preferable in view of high refractive index.

[ solution 39]

Among the above-mentioned structural units, those shown in the following group [ N ] are preferable in view of low-cost raw material supply and ease of synthesis.

[ solution 40]

The following structural units are most preferable from the viewpoint of low-cost raw material supply and low birefringence.

[ solution 41]

The thermoplastic resin having the structural unit (1) can be produced, for example, by polymerization of the compound (f) of the present disclosure or the like.

(structural Unit (2))

The structural unit (2) is represented by the following formula (2).

The thermoplastic resin preferably contains the structural unit (2) from the viewpoint of a balance of glass transition temperatures which is preferable because the refractive index is high and the molding processability is good, and from the viewpoint of low-cost raw material supply.

[ solution 42]

Wherein R is ¹ Represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms and having or not having a substituent;

L ³ and L ⁴ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may have a substituent, an arylene group having 4 to 10 carbon atoms, which may have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may have a substituent; o represents an integer of 0 to 4; p represents an integer of 0 to 4.

From the viewpoints of high refractive index and ease of synthesis, L ³ And L ⁴ Each independently is preferably an alkylene group having 1 to 4 carbon atoms with or without a substituent, and more preferably an ethylene group.

From the viewpoint of high refractive index and ease of synthesis, o and p are each independently preferably 0 or 1.

From the viewpoint of ease of synthesis, the structural unit (2) is preferably represented by the following formula (2-1).

[ solution 43]

R ³ 、R ⁴ 、R ⁷ and R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

L ³ and L ⁴ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may have a substituent; o represents 0 or 1; p represents 0 or 1.

From the viewpoint of ease of synthesis, the structural unit (2) is preferably a symmetrical structure and is represented by the following formula (2-2).

[ solution 44]

Wherein R is ¹ Represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms with or without a substituent, R ⁴ And R ⁷ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

The structural unit (2) is preferably represented by the following formula (2-3) from the viewpoints of low-cost raw material supply and high refractive index.

[ solution 45]

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms with or without a substituent;

L in the above formula (2-3) ³ Or L ⁴ The alkylene group (b) has a tendency to decrease the refractive index as it becomes longer, and therefore, preferably, p and o are 0; o or p is 1, L ³ Or L ⁴ Is an alkylene group having 1 to 2 carbon atoms. From the viewpoint of ease of synthesis, it is particularly preferable that the number of carbon atoms of the alkylene group is 2.

R in the above formula (2-3) is represented by a formula of ¹ Preferably a direct bond, an oxygen atom.

R in the above formula (2-3) is defined as a preferable glass transition temperature which is considered to be excellent in synthesis easiness and molding processability ¹ The aromatic vinyl compound is preferably a methylene group, an alkylmethylene group having 2 to 40 carbon atoms, or a dialkylmethylene group having 3 to 40 carbon atoms, and more preferably an alkylmethylene group having 2 to 40 carbon atoms.

From the viewpoint of a high refractive index, R in the above formula (2-3) is more preferable ¹ Is methylene.

From the viewpoint of adjusting to a preferable glass transition temperature which is considered to be good in synthesis easiness and molding processability, R in the above formula (2-3) is more preferable ¹ Is an alkylmethylene group having 2 to 40 carbon atoms. From the viewpoint of lower cost of raw material supply, the number of carbon atoms of the alkylmethylene group is preferably 2 to 4. From the viewpoint of improving moldability, the number of carbon atoms of the alkylmethylene group is preferably 3 or more, more preferably 10 or more, and still more preferably 12 or more. From the viewpoint of refractive index, the number of carbon atoms of the alkylmethylene group is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less. The number of carbon atoms of the alkylmethylene group is preferably 7 to 15 from the viewpoint of improving moldability and balance between refractive index.

From the viewpoint of thermal stability, R in the above formula (2-3) ¹ Preferably a C3-C40 dialkylmethylene group. The number of carbon atoms of the dialkylmethylene group is preferably 5 or more, more preferably 10 or more from the viewpoint of moldabilityMore preferably 20 or more. From the viewpoint of refractive index, the number of carbon atoms of the dialkylmethylene group is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less. The number of carbon atoms of the dialkylmethylene group is preferably 3 to 10 from the viewpoint of ease of synthesis.

In view of high refractive index, R in the above formula (2-3) ⁴ Preferably a hydrogen atom.

R in the above formula (2-3) is a group represented by the following formula ⁴ Preferably methyl.

In view of high refractive index, o and p in the above formula (2-3) are preferably 0.

In view of a preferable glass transition temperature which is considered to be good in moldability, o and p in the above formula (2-3) are preferably 1.

Specific examples of the structural unit (2) include those shown in the following group [ OO ].

[ solution 46]

Among these structural units, those shown in the following group [ P ] are preferable.

[ solution 47]

The thermoplastic resin having the structural unit (2) can be produced, for example, by polymerization of a monomer represented by the following formula (g).

[ solution 48]

Wherein R in the formula (g) ¹ ～R ⁹ 、L ³ 、L ⁴ O and p are each independently as defined in the above formula (2)R ¹ ～R ⁹ 、L ³ 、L ⁴ O and p are the same.

Specific examples of the monomer represented by the formula (g) include the following monomers.

[ solution 49]

Since the following monomer can impart a high refractive index and has a glass transition temperature that is considered to be good in molding processability, it is preferable to use the monomer in combination with the structural unit (8) described later because the glass transition temperature can be lowered and molding processability can be improved without significantly impairing the refractive index as compared with the case of using the structural unit (8) alone. The thermoplastic resin containing these structural units may not contain the structural unit (1).

[ solution 50]

(structural Unit (3))

The structural unit (3) is represented by the following formula (3).

The structural unit (3) has an axially asymmetric structure and has a high refractive index because it has aromatic rings densely in the molecular skeleton. Further, since the interaction between the aromatic rings is inhibited in the structural unit (3), the glass transition temperature is low and the moldability is excellent. The thermoplastic resin preferably contains the structural unit (3) from the viewpoint of a preferable glass transition temperature which is considered to be high in refractive index and good in molding processability.

[ solution 51]

Wherein R is ¹⁰ ～R ²¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and having or not having a substituent, an alkyl group having or not having a substituentAn aryl group having 3 to 14 carbon atoms which may have no substituent, an acyl group having 1 to 10 carbon atoms which may have no substituent, an alkoxy group having 1 to 10 carbon atoms which may have no substituent, an aryloxy group having 3 to 14 carbon atoms which may have no substituent, an acyloxy group having 1 to 10 carbon atoms which may have no substituent, an amino group having or not having substituent, an alkenyl group having 2 to 10 carbon atoms which may have substituent, an alkynyl group having 2 to 10 carbon atoms which may have substituent, a silicon atom having substituent, a halogen atom, a nitro group or a cyano group;

L ⁵ and L ⁶ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms, which may or may not have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may or may not have a substituent;

q represents an integer of 0 to 4; r represents an integer of 0 to 4.

L in the formula (3) from the viewpoints of ease of synthesis and low-cost synthesis ⁵ And L ⁶ Preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group. L in the formula (3) ⁵ And L ⁶ The structural unit which is an ethylene group is represented by the following formula (3-1).

[ solution 52]

Wherein R is ¹⁰ ～R ²¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a pharmaceutically acceptable carrier, a salt thereof, a carrier,a silicon atom, a halogen atom, a nitro group or a cyano group having a substituent;

q represents an integer of 0 to 4; r represents an integer of 0 to 4.

From the viewpoint of ease of synthesis, the structural unit (3) is more preferably a symmetrical structure and is represented by the following formula (3-2).

[ Hua 53]

Wherein R is ¹⁰ ～R ¹⁵ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

q represents an integer of 0 to 4; r represents an integer of 0 to 4.

The structural unit (3) is preferably represented by the following formula (3-3) from the viewpoints of ease of synthesis and low-cost raw material supply.

[ solution 54]

Wherein R is ¹⁰ 、R ¹³ And R ¹⁴ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, an aryl group having 3 to 14 carbon atoms and optionally having a substituent, an acyl group having 1 to 10 carbon atoms and optionally having a substituent, an alkoxy group having a substituentOr an unsubstituted aryloxy group having 3 to 14 carbon atoms, an unsubstituted acyloxy group having 1 to 10 carbon atoms, an unsubstituted amino group, an unsubstituted alkenyl group having 2 to 10 carbon atoms, an unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted silicon atom, a halogen atom, a nitro group or a cyano group;

q represents an integer of 0 to 4;

r represents an integer of 0 to 4.

From the viewpoint of ease of synthesis, R is preferred ¹⁰ 、R ¹³ And R ¹⁴ At least one of which is a hydrogen atom, more preferably R ¹⁰ 、R ¹³ 、R ¹⁴ At least two of which are hydrogen atoms.

As R, the composition is obtained from the viewpoint of compatibility between low-cost raw material supply and high refractive index ¹⁰ 、R ¹³ And R ¹⁴ Preferably, each independently represents a hydrogen atom, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 3 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, a halogen atom, a nitro group, or a cyano group.

R is a compound having a balance between color resistance, high refractive index and ease of synthesis ¹⁰ 、R ¹³ And R ¹⁴ Preferably, each independently represents a hydrogen atom, an aryl group having 3 to 14 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, an aryloxy group having 3 to 14 carbon atoms which may have a substituent, an acyloxy group having 1 to 10 carbon atoms which may have a substituent, or a cyano group.

As the structural unit (3), the structural unit shown in the following group [ Q ] is preferable in view of obtaining a balance between the coloring resistance, the high refractive index and the ease of synthesis.

[ solution 55]

Among the above-mentioned structural units, those shown in the following group [ R ] are preferable in view of ease of synthesis and low-cost supply of raw materials.

[ solution 56]

The thermoplastic resin having the structural unit (3) can be produced, for example, by polymerization of a monomer represented by the following formula (h).

[ solution 57]

Wherein R in the formula (h) ¹⁰ ～R ²¹ 、L ⁵ 、L ⁶ Q and R are each independently R in the above formula (3) ¹⁰ ～R ²¹ 、L ⁵ 、L ⁶ Q and r are the same.

Specific examples of the monomer represented by the formula (h) include the following monomers.

[ solution 58]

Since the following monomer has a high refractive index and a glass transition temperature that is considered to be good in molding processability, it is preferable to use the monomer in combination with the structural unit (8) described later because the glass transition temperature can be lowered and molding processability can be improved without significantly impairing the refractive index as compared with the case of using the structural unit (8) alone. The thermoplastic resin containing these structural units may not contain the structural unit (1).

[ chemical 59]

(structural Unit (4))

The structural unit (4) is represented by the following formula (4).

In the structural unit (4), since the fluorene skeleton is located at a position perpendicular to the main chain, birefringence is small, and it is excellent in view of moldability. The thermoplastic resin preferably contains the structural unit (4) from the viewpoint of birefringence and molding processability.

[ solution 60]

Wherein V represents an arylene group with or without a substituent;

s represents an integer of 0 to 4; t represents an integer of 0 to 4.

s and t each independently represent an integer of 0 to 4, preferably 0 to 3, and more preferably 0 to 2, from the viewpoint of synthesis of a high refractive index resin.

S and t are each independently particularly preferably 0 or 1 from the viewpoint of adjusting to a preferable glass transition temperature which is considered to be good in moldability, and from the viewpoint of low-cost synthesis.

The structural unit (4) is preferably represented by the following formula (4-1) from the viewpoints of ease of synthesis and synthesis of a resin having a high refractive index.

[ solution 61]

Wherein V is a phenylene group or a naphthylene group with or without a substituent; the substituent of V represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent; s represents 0 or 1; t represents 0 or 1.

The structural unit (4) is preferably represented by the following formula (4-2) from the viewpoints of ease of synthesis and adjustment to a preferable glass transition temperature which is considered to be good in moldability.

The structural unit (4) is preferably represented by the following formula (4-3) from the viewpoints of ease of synthesis and refractive index.

[ solution 62]

Wherein R is ³³ Represents a hydrogen atom, a methyl group or a phenyl group; s represents 0 or 1; t represents 0 or 1.

[ solution 63]

Wherein s represents 0 or 1; t represents 0 or 1.

Specific examples of the structural unit (4) include the following structural units.

[ solution 64]

The thermoplastic resin having the structural unit (4) can be produced, for example, by polymerization of a monomer represented by the following formula (i).

[ solution 65]

Wherein V, L in the formula (i) ⁷ 、L ⁸ S and t are each independently V, L in the above formula (4) ⁷ 、L ⁸ S and t are the same.

Specific examples of the monomer represented by the formula (i) include the following monomers.

[ chemical formula 66]

(structural Unit (5))

The structural unit (5) is represented by the following formula (5).

Since the structural unit (5) has a large negative birefringence, the thermoplastic resin containing the structural unit (5) can have a reduced birefringence and is excellent in molding processability. Since the structural unit (5) has a low photoelastic coefficient, the thermoplastic resin containing the structural unit (5) is less likely to change in retardation due to stress, and is preferable in view of moldability and reliability.

[ solution 67]

Wherein A is ¹ ～A ⁸ Each independently represents ═ CH-or ═ N —;

R ²² 、R ²³ and R ²⁴ Each independently represents a direct bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or a carbon atom which may have a substituent4 to 10 arylene groups, C6 to C12 aralkylene groups with or without substituents, or groups in which 2 or more groups selected from the group consisting of C1 to C10 alkylene groups with or without substituents and C4 to C10 arylene groups with or without substituents are linked by oxygen atoms, nitrogen atoms with or without substituents, or carbonyl groups;

R ²⁵ ～R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

R ²⁵ ～R ³² at least 2 adjacent groups of (a) may be bonded to each other to form a ring;

v represents an integer of 0 to 5.

R ²² 、R ²³ And R ²⁴ Specific examples of the "arylene group having 4 to 10 carbon atoms" in the "arylene group having 4 to 10 carbon atoms which may have a substituent(s)" include, but are not limited to, phenylene groups such as 1, 2-phenylene, 1, 3-phenylene and 1, 4-phenylene; naphthylene groups such as 1, 5-naphthylene group and 2, 6-naphthylene group; heteroarylene groups such as 2, 5-pyridylene and 2, 4-furanylene.

R ²² 、R ²³ And R ²⁴ In the above formula, "aralkylene group having 6 to 10 carbon atoms" in "aralkylene group having 6 to 12 carbon atoms with or without substituent(s)" includes, for example, a group composed of an aromatic ring structure and 2 linear or branched alkylene groups bonded to arbitrary 2 positions of the aromatic ring structure. The aromatic ring structure can be a hydrocarbon ring such as a benzene ring, a naphthalene ring and the likeThe structure may be a heterocyclic structure such as a furan ring or a pyridine ring.

Specific examples of the C6-10 aralkylene group include, but are not limited to, those shown in the following group [ G ].

[ solution 68]

The structural unit (5) is preferably represented by the following general formula (5-1) from the viewpoints of ease of synthesis and low-cost raw material supply.

[ solution 69]

Wherein A is ⁴ And A ⁵ Each independently represents ═ CH-or ═ N-;

R ²² 、R ²³ and R ²⁴ Each independently represents a group in which at least 2 groups selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms which may or may not have a substituent, an aralkylene group having 6 to 12 carbon atoms which may or may not have a substituent, and an alkylene group having 1 to 10 carbon atoms which may or may not have a substituent, an arylene group having 4 to 10 carbon atoms and an aralkylene group having 6 to 12 carbon atoms which may or may not have a substituent are linked to each other by an oxygen atom, a nitrogen atom having or not having a substituent, or a carbonyl group;

R ²⁵ ～R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, an aryl group having 3 to 14 carbon atoms and optionally having a substituent, an acyl group having 1 to 10 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 10 carbon atoms and optionally having a substituent, an aryloxy group having 3 to 14 carbon atoms and optionally having a substituent, an acyloxy group having 1 to 10 carbon atomsAn amino group having or not having a substituent, an alkenyl group having or not having a substituent and having 2 to 10 carbon atoms, an alkynyl group having or not having a substituent and having 2 to 10 carbon atoms, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

v represents an integer of 0 to 2.

R ²² 、R ²³ And R ²⁴ Independently of each other, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms, with or without a substituent.

The structural unit (5) is preferably represented by the following formula (5-2) from the viewpoints of ease of synthesis and low-cost supply of raw materials.

[ solution 70]

Wherein A is ⁵ Each independently represents ═ CH-or ═ N-;

R ²² 、R ²³ and R ²⁴ Each independently represents a direct bond or an alkylene group having 1 to 3 carbon atoms which may have a substituent;

R ²⁷ 、R ²⁸ 、R ³⁰ and R ³¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

v represents an integer of 0 to 2.

The structural unit (5) is preferably represented by the following formula (5-3) from the viewpoints of ease of synthesis and low-cost raw material supply.

[ solution 71]

Wherein R is ²² 、R ²³ And R ²⁴ Each independently represents a direct bond, a methylene group or an ethylene group.

The structural unit (5) is preferably represented by the following formula (5-4) from the viewpoints of ease of synthesis and synthesis of a resin having a high refractive index.

[ chemical formula 72]

From the viewpoint of synthesis of a high refractive index resin, the structural unit (5) is preferably represented by the following formula (5-5).

[ solution 73]

As the specific structural unit (5), the following structural units are preferable in view of low-cost raw material supply.

[ chemical formula 74]

In the structural group shown below, aromatic rings are densely introduced to form a rigid skeleton, and therefore, the low photoelastic coefficient is exhibited. The thermoplastic resin containing a structural unit having a low photoelastic coefficient is less likely to cause a change in retardation due to stress, and is preferable in view of moldability and reliability.

[ solution 75]

The thermoplastic resin having the structural unit (5) can be produced, for example, by polymerization of a monomer represented by the following formula (j).

[ 76]

Wherein A in the formula (j) ¹ ～A ⁸ 、R ²² ～R ³² And v are each independently A in the above formula (5) ¹ ～A ⁸ 、R ²² ～R ³² And v are the same, J ¹ And J ² Each independently represents a polymerization reactive group.

J ¹ And J ² Specific examples of the polymerization reactive group include, but are not limited to, those related to B in the above formula (f) ¹ And B ² The polymerization reactive group in (1) is the same group. From the viewpoint of being usable in a polyester, a polycarbonate or a polyester carbonate as a preferable polymer, a hydroxyl group-containing group, an ester group, or a hydroxyl ester group, a carboxyl group-containing group, an acid halide-containing group is preferable.

J ¹ And J ² May be the same or different. In different cases, as J ¹ And J ² Examples of the combination of (b) include a combination of a hydroxymethyl group and an ethoxycarbonyl group, a combination of a 2- (2-hydroxyethoxy) carbonyl group and a carboxyl group, and a combination of a 2- (2-hydroxyethoxy) carbonylethyl group and a carboxyethyl group.

For the reason that the production of the monomer represented by formula (J) tends to be carried out in a short process, J is preferable ¹ And J ² The same is true.

The monomer represented by the formula (j) may be a monomer having 2-valent oligofluorene as a repeating unitThe polymer of (4) is used as a raw material, but the polymerization reactive group is preferably only J ¹ And J ² In the 2 nd place, it is preferable that a substituent which functions as a polymerization reactive group under polymerization conditions for producing various resin compositions is not contained in R ²⁵ ～R ³² In (1).

In a preferred embodiment, J in formula (J) ¹ And J ² Is a hydroxyl group. J. the design is a square ¹ And J ² The monomer which is a hydroxyl group is a monomer which can be generally used in polyesters, polycarbonates and polyester carbonates as preferred thermoplastic resins because of its good optical properties. J. the design is a square ¹ And J ² The monomer which is a hydroxyl group is represented by the following formula (j 1).

[ solution 77]

In another preferred embodiment, J in formula (J) ¹ And J ² Is an ester group. J. the design is a square ¹ And J ² Since the ester-based monomer has good optical properties, it can be used in general for polyesters and polyester carbonates, which are preferred thermoplastic resins.

The ester group is preferably a phenoxycarbonylalkyl group, because the diester compound, dihydroxy compound and carbonic acid diester can be reacted under the same conditions to synthesize a polyester carbonate as a preferable thermoplastic resin in one step, because the activity of the ester group is increased and the ester exchange reaction is easily progressed. In particular, 2- (phenoxycarbonyl) methyl, 2- (phenoxycarbonyl) ethyl, and 2- (phenoxycarbonyl) propyl can be introduced by using 2-bromophenyl acetate, phenyl acrylate, and phenyl methacrylate; introduction methods based on transesterification starting from 2-bromoacetate, 2-chloroacetate, 2-iodoacetate, acrylates, methacrylates are particularly preferred.

J ¹ And J ² The monomer which is an ester group is represented by, for example, the following formula (j 2).

[ solution 78]

Wherein, J ³ And J ⁴ Each independently represents an organic substituent having 1 to 10 carbon atoms or a halogen atom.

J ³ And J ⁴ Specific examples of the organic substituent having 1 to 10 carbon atoms include, but are not limited to, a linear alkoxy group such as a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a n-pentoxy group, a n-hexoxy group, and a n-decoxy group; branched alkoxy groups such as isopropoxy, 2-methylpropoxy, 2-dimethylpropoxy, and 2-ethylhexyloxy; cyclic alkoxy groups such as cyclopropyloxy, cyclopentyloxy, cyclohexyloxy and cyclooctyloxy; aryloxy groups such as phenoxy, 1-naphthyloxy, and 2-naphthyloxy; heteroaryl comprising a 1-imidazolyl group: heteroaryloxy groups such as 2-pyridyloxy and 2-furanyloxy; aralkyloxy groups such as benzyloxy, 2-phenylethoxy, and p-methoxybenzyloxy.

J is a group capable of efficiently synthesizing a polyester and a polyester carbonate by removing a low-boiling alcohol generated in the transesterification with a dihydroxy compound ³ And J ⁴ Methyl and ethyl are preferred.

J is a polymer which can be synthesized in one step from the viewpoint that a polyester carbonate which is a preferable polymer can be synthesized by adding a diester compound, a dihydroxy compound and a carbonic acid diester at one time to a reactor for the reason of easiness of the transesterification reaction, and ³ and J ⁴ Aryl groups are preferred. In particular, phenyl is particularly preferred for reasons of low molecular weight and ability to be distilled off as phenol after the synthesis of the polyester carbonate。

J is used in the method for producing a thermoplastic resin described later ³ And J ⁴ In the case of an aryl compound, the diaryl carbonates described later are preferably used as the carbonic acid diester from the viewpoint of reactivity at the time of polymerization, and J is more preferably used from the viewpoint of easy removal of by-products ³ And J ⁴ The aryl group of (a) is the same as the aryl group in the diaryl carbonate group.

From the viewpoint that the polymerization reactivity is good and the thermoplastic resin can be obtained by relatively simple equipment such as solution polymerization and interfacial polymerization, J ³ And J ⁴ The acid chloride-containing group is preferable, and acid chloride and acid bromide are more preferable because they can be industrially produced at low cost.

Specific examples of the monomer represented by the formula (j) include the following monomers.

[ solution 79]

[ solution 80]

[ solution 81]

[ chemical 82]

(structural Unit (6))

The structural unit (6) is represented by the following formula (6).

The thermoplastic resin preferably contains the structural unit (6) from the viewpoint of low-cost raw material supply.

[ solution 83]

Wherein, K ¹ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

u represents an integer of 0 to 4; when u is 2 or more, each K ¹ May be the same or different.

From the viewpoint of low-cost synthesis, u in formula (6) is preferably an integer of 0 to 2.

The structural unit (6) is preferably represented by the following formula (6-1) or (6-2) from the viewpoint of low-cost raw material supply.

[ solution 84]

The thermoplastic resin having the structural unit (6) can be produced, for example, by polymerization of a monomer represented by the following formula (k).

[ solution 85]

Wherein, K in the formula (K) ¹ And u are each independently K in the above formula (6) ¹ Same as u, M ¹ And M ² Each independently is substituted or unsubstitutedAn alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a phenyl group or a halogen atom.

Specific examples of the monomer represented by the formula (k) include the following monomers.

[ solution 86]

(structural Unit (7))

The structural unit (7) is represented by the following formula (7).

From the viewpoint of low-cost raw material supply and high-refractive index resin synthesis, the thermoplastic resin preferably contains the structural unit (7).

[ solution 87]

Wherein, K ² Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group;

w represents an integer of 0 to 4; when w is 2 or more, each K ¹ May be the same or different.

In view of low cost synthesis, w in formula (7) is preferably an integer of 0 to 2.

The structural unit (7) is represented by the following formula (7-1) or (7-2) from the viewpoint of low-cost raw material supply.

[ solution 88]

The thermoplastic resin having the structural unit (7) can be produced, for example, by polymerization of a monomer represented by the following formula (l).

[ solution 89]

Wherein, K in the formula (l) ² And w are each independently K in the above formula (7) ² Same as w, N ¹ And N ² Each independently represents an alkyloxy group having 1 to 10 carbon atoms, a hydrogen atom, a phenoxy group or a halogen atom, with or without a substituent.

Specific examples of the monomer represented by the formula (l) include the following monomers.

[ solution 90]

(structural Unit (8))

The structural unit (8) is represented by the following formula (8).

The thermoplastic resin preferably contains the structural unit (8) from the viewpoint of adjusting the glass transition temperature which is preferable in view of ease of synthesis and molding processability, and from the viewpoint of synthesis of the high-refractive-index resin.

[ solution 91]

Wherein one of the 2 connecting bonds in the formula is bonded to any one of the carbon atoms of the substitution position numbers 1-6, and the other connecting bond is bonded to any one of the carbon atoms of the substitution position numbers 8-13;

Specific examples of the structural unit (8) include structural units represented by the following group [ S ].

[ solution 92]

Among the above-mentioned structural units, those shown in the following group [ T ] are preferable in view of the balance between ease of synthesis and high refractive index.

[ chemical No. 93]

Among the above-mentioned structural units, those shown in the following group [ U ] are preferable in view of ease of synthesis and high refractive index.

[ solution 94]

Among the above-mentioned structural units, those shown in the following group [ V ] are preferable from the viewpoints of low-cost raw material supply and ease of synthesis.

[ solution 95]

The following structural units are preferred in view of low-cost raw material supply, ease of synthesis, and low birefringence.

[ solution 96]

The thermoplastic resin having the structural unit (8) can be produced, for example, by polymerization of a monomer represented by the following formula (m).

[ solution 97]

Wherein, B ⁷ And B ⁸ Each independently represents a polymerization reactive group;

B ⁷ bonded to any one of the carbon atoms of substitution position numbers 1 to 6;

B ⁸ bonded to any one of carbon atoms of substitution position numbers 8 to 13;

unbound B in the carbon atoms of substitution positions 1-6, 8-13 ⁷ Or B ⁸ Each of which is independently bonded to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, an aryl group having 3 to 14 carbon atoms and optionally having a substituent, an acyl group having 1 to 10 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 10 carbon atoms and optionally having a substituent, an aryloxy group having 3 to 14 carbon atoms and optionally having a substituent, an acyloxy group having 1 to 10 carbon atoms and optionally having a substituent, an amino group having or not having a substituent, an alkenyl group having 2 to 10 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 10 carbon atoms and optionally having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a nitro groupA cyano group.

B ⁷ And B ⁸ Specific examples of the polymerization reactive group include, but are not limited to, those related to B in the above formula (f) ¹ And B ² The polymerization reactive group in (1) is the same group. From the viewpoint of being usable in polyesters, polycarbonates and polyester carbonates as preferable polymers, hydroxyl groups, ester groups, carboxyl groups, acid halides and hydroxyl ester groups are preferable.

Specific examples of the monomer represented by the formula (m) include the following monomers. In the following compounds, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Cl represents a chlorine group, and Br represents a bromine group.

[ solution 98]

The thermoplastic resin having the structural unit (8) has a very high refractive index and heat resistance. From this viewpoint, as an example of a preferable thermoplastic resin, there is one having a repeating unit represented by the above formula (X) and at least a part of the repeating unit represented by the above formula (X) is Q ¹ And Q ² At least one of which is a repeating unit of the structural unit (8).

The thermoplastic resin is a resin containing B at least a part of which is represented by the formula (m) ⁷ And B ⁸ In the case of a polycarbonate, polyester or polyestercarbonate obtained from a dihydroxy compound which is a hydroxy compound, the thermoplastic resin has Q in the formula (X) ¹ Is a repeating unit of the structural unit (8). When a of the repeating unit is 1, Q ² Any of the structural units (1) to (7) and other structural units may be used.

The thermoplastic resin is a resin containing B at least a part of which is represented by the formula (m) ⁷ And B ⁸ In the case of a polyester or polyester carbonate obtained as a dicarboxylic acid compound which is an ester, carboxyl, acid halide or hydroxy ester compound, the thermoplastic resin has Q in the formula (X) ² Is a repeating unit of the structural unit (8). Q of the repeating unit ¹ Can be a knotAny one of the structural units (1) to (7) and other structural units.

Q in the formula (X) in the thermoplastic resin ¹ A and Q ² Any one or more of them may have two or more kinds of repeating units different from each other.

[ other structural units ]

Examples of the other structural unit include structural units based on other dihydroxy compounds and structural units based on other dicarboxylic acid compounds.

Examples of the other dihydroxy compound include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, tricyclo [5.2.1.02,6] decanedimethanol, cyclohexane-1, 4-dimethanol, decalin-2, 6-dimethanol, norbornanedimethanol, pentacyclopentadecane dimethanol, cyclopentane-1, 3-dimethanol, spiroglycol, isosorbide, isomannide, isoidide, and the like. These may be used alone or in combination of two or more.

In the thermoplastic resin, the proportion of the structural unit based on the other dihydroxy compound is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less, based on 100 mol% of the total of the structural units based on all dihydroxy compounds.

Examples of the other dicarboxylic acid compounds include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid; anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, 2 '-bis (carboxymethoxy) -1, 1' -binaphthyl, 9-bis (carboxymethyl) fluorene, 9-bis (2-carboxyethyl) fluorene, 9-bis (1-carboxypropyl) fluorene, polycyclic aromatic dicarboxylic acids such as 9, 9-bis (2-carboxypropyl) fluorene, 9-bis (2-carboxy-1-methylethyl) fluorene, 9-bis (2-carboxy-1-methylpropyl) fluorene, 9-bis (2-carboxybutyl) fluorene, 9-bis (2-carboxy-1-methylbutyl) fluorene, 9-bis (5-carboxypentyl) fluorene and 9, 9-bis (carboxycyclohexyl) fluorene; biphenyldicarboxylic acids such as 2, 2' -biphenyldicarboxylic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid and 2, 6-decahydronaphthalenedicarboxylic acid; ester-forming derivatives of these dicarboxylic acids; and so on. Examples of the ester-forming derivative include acid chlorides; methyl ester, ethyl ester, phenyl ester, and the like. These compounds may be used alone or in combination of two or more.

In the thermoplastic resin, the proportion of the structural unit based on the other dicarboxylic acid compound is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less, based on 100 mol% of the total of the structural units based on all the dicarboxylic acid compounds.

(composition ratio)

The content ratio of the structural unit (1) and the content ratios of the structural units (2) to (8) in the thermoplastic resin are preferably within a range in which a preferable refractive index and a preferable glass transition temperature described later are exhibited.

The content ratio of the structural unit (1) is preferably 2.5 mol% or more, more preferably 5 mol% or more, further preferably 7.5 mol% or more, further preferably 12.5 mol% or more, and particularly preferably 25 mol% or more, based on the total molar amount of all the structural units based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonic acid esters in the thermoplastic resin, from the viewpoints of high refractive index, ensuring melt processability, mechanical strength, and molding processability.

From the same viewpoint, the content ratio of the structural unit (1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 25% by mass or more, and particularly preferably 45% by mass or more, based on the total mass of the thermoplastic resin based on all the dihydroxy compound, all the dicarboxylic acid compound, and all the carbonate ester in the thermoplastic resin. From the same viewpoint, the content ratio of the structural units (2) to (8) is preferably more than 0 mol%, more preferably 1 mol% or more, further preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 15 mol% or more, based on the total molar amount of all the structural units based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonic acid esters in the thermoplastic resin. Further, it is preferably 85 mol% or less, more preferably 75 mol% or less, further preferably 70 mol% or less, further preferably 65 mol% or less, and particularly preferably 60 mol% or less.

From the same viewpoint, the content ratio of the structural units (2) to (8) is preferably more than 0% by mass, more preferably 1% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on the total mass of the thermoplastic resin based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonate esters in the thermoplastic resin. Further, it is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less.

On the other hand, there is also a use for achieving the object of effectively increasing the refractive index while maintaining the particularly preferable glass transition temperature of the existing material by containing a small amount of the structural unit (1) in the existing material. In this use, the content of the structural unit (1) is small, and therefore, a resin can be obtained without significantly changing the physical properties of other resins of conventional materials, which is also preferable from the viewpoint.

From this viewpoint, the content ratio of the structural unit (1) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, further preferably 1 mol% or more, further preferably 2 mol% or more, and particularly preferably 4 mol% or more, based on the total molar amount of all the structural units based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonic acid esters in the thermoplastic resin. Further, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, further preferably 15 mol% or less, and particularly preferably 10 mol% or less. From the same viewpoint, the content of the structural unit (1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 4% by mass or more, and particularly preferably 8% by mass or more, based on the total mass of the thermoplastic resin based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonate esters in the thermoplastic resin. And is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less.

From the same viewpoint, the content ratio of the structural units (2) to (8) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, further preferably 30 mol% or more, and particularly preferably 35 mol% or more, based on the total molar amount of all the structural units based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonic acid esters in the thermoplastic resin. Further, it is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, further preferably 65 mol% or less, and particularly preferably 60 mol% or less.

From the same viewpoint, the content ratio of the structural units (2) to (8) is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, further preferably 65% by mass or more, and particularly preferably 70% by mass or more, based on the total mass of the thermoplastic resin based on all the dihydroxy compounds, all the dicarboxylic acid compounds, and all the carbonate esters in the thermoplastic resin. Further, it is preferably 99.9% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 96% by mass or less, and particularly preferably 94% by mass or less.

(refractive index: nD, glass transition temperature: Tg)

The refractive index (nD) of the thermoplastic resin at a wavelength of 589nm as measured at 20 ℃ is preferably 1.620 or more, more preferably 1.645 or more, still more preferably 1.650 or more, yet more preferably 1.660 or more, and particularly preferably 1.680 or more. When nD is equal to or higher than the lower limit value, spherical aberration of a lens using a thermoplastic resin can be reduced, and the focal length of the lens can be shortened.

On the other hand, there is also a use for achieving the object of effectively increasing the refractive index while maintaining the particularly preferable glass transition temperature of the existing material by containing a small amount of the structural unit (1) in the existing material. In this use, the content of the structural unit (1) is small, and therefore, a resin can be obtained without significantly changing the physical properties of other resins of conventional materials, which is also preferable from the viewpoint. From this point of view, nD of the thermoplastic resin measured at 20 ℃ is preferably 1.600 or more, more preferably 1.610 or more, further preferably 1.620 or more, further preferably 1.630 or more, and particularly preferably 1.645 or more.

In one embodiment, the glass transition temperature (Tg) of the thermoplastic resin is preferably 100 to 180 ℃, more preferably 100 to 175 ℃, even more preferably 100 to 170 ℃, and particularly preferably 100 to 160 ℃. When Tg is not less than the lower limit, heat resistance is excellent, and when Tg is not more than the upper limit, moldability is excellent. In a particularly preferred glass transition temperature range, the composition has high fluidity while maintaining a minimum heat resistance, and is extremely excellent in moldability.

In another embodiment, the glass transition temperature (Tg) of the thermoplastic resin is preferably 110 to 180 ℃, more preferably 120 to 180 ℃, even more preferably 130 to 180 ℃, and particularly preferably 135 to 180 ℃. When the Tg is not less than the above lower limit, the heat resistance is excellent, and when the Tg is not more than the above upper limit, the moldability is excellent. A particularly preferred glass transition temperature range is preferred because it is a resin having high heat resistance while maintaining the minimum fluidity, and therefore, the balance between heat resistance and moldability is excellent.

As described above, in order to obtain a thermoplastic resin having a high refractive index and a preferable glass transition temperature, it is preferable that the thermoplastic resin contains a structural unit (hereinafter, also referred to as "high n structural unit") which can provide a very high refractive index and a glass transition temperature which is considered to be good in molding processability.

The high n-structural unit is preferably a structural unit having a refractive index of 1.67 or more, more preferably a structural unit having a refractive index of 1.68 or more, still more preferably a structural unit having a refractive index of 1.69 or more, and particularly preferably a structural unit having a refractive index of 1.70 or more, of a thermoplastic resin composed of only the structural unit and a carbonate bond or an ester bond, that is, a linking group.

The glass transition temperature of the thermoplastic resin composed of only the high n structural unit and the carbonate bond or the ester bond, that is, the linking group is preferably 50 to 295 ℃, more preferably 60 to 270 ℃, still more preferably 70 to 250 ℃, and most preferably 80 to 150 ℃.

By using a high n-structural unit satisfying the above refractive index and glass transition temperature, the refractive index of the thermoplastic resin can be effectively increased, and a thermoplastic resin having a preferable refractive index and glass transition temperature can be obtained. Examples of the high n structural unit satisfying the refractive index and the glass transition temperature include 2,12DNFE:2, 12-bis (2-hydroxyethoxy) dinaphthofuran of the structural unit (1).

The high n-structural unit is preferably a structural unit having a refractive index of 1.70 or more, more preferably a structural unit having a refractive index of 1.71 or more, and particularly preferably a structural unit having a refractive index of 1.715 or more, which is a thermoplastic resin composed of only the structural unit and a carbonate bond or an ester bond, that is, a linking group. Further, the glass transition temperature of the thermoplastic resin composed of only the high n-structural unit and the carbonate bond or the ester bond, that is, the linking group is preferably 350 ℃ or lower, particularly preferably 340 ℃ or lower, and most preferably 330 ℃ or lower. Examples of the high n structural unit satisfying the refractive index and the glass transition temperature include 2,12DNF:2, 12-dihydroxydinaphthofuran of the structural unit (8).

(Abbe number: v D)

The abbe number (ν D) of the thermoplastic resin is preferably 23 or less, more preferably 22 or less, and further preferably 21 or less.

Abbe's number was calculated from refractive indices measured at 20 ℃ at wavelengths of 486nm, 589nm, and 656nm using the following equation.

νD＝(nD-1)/(nF-nC)

Wherein nD is the refractive index of 589nm wavelength; nC is the refractive index of 656nm wavelength; nF is the refractive index at a wavelength of 486 nm.

(coefficient of photoelasticity)

The absolute value of the photoelastic coefficient of the thermoplastic resin is preferably 130X 10 ^-12 Pa ^-1 Hereinafter, more preferably 100 × 10 ^-12 Pa ^-1 Hereinafter, more preferably 80 × 10 ^-12 Pa ^-1 The following, more preferably 60X 10 ^-12 Pa ^-1 The following, particularly preferably 40X 10 ^-12 Pa ^-1 The following. When the photoelastic coefficient is equal to or less than the upper limit value, the optical strain of the lens using the thermoplastic resin is reduced. The photoelastic coefficient was measured by a device in which a birefringence measurement device including a He — Ne laser, a polarizing element, a compensation plate, an analyzer, and a photodetector was combined with a vibration-type viscoelasticity measurement device.

(reduced viscosity)

If the reduced viscosity of the thermoplastic resin is too low, the heat resistance, chemical resistance, abrasion resistance and mechanical strength of the resulting molded article may be lowered. Therefore, when used for a lens, the reduced viscosity of the thermoplastic resin is preferably 0.15dL/g or more, more preferably 0.20dL/g or more, and still more preferably 0.25dL/g or more.

On the other hand, if the reduced viscosity of the thermoplastic resin is too high, the following tendency is exhibited: the fluidity at the time of molding is lowered, and the productivity and moldability are lowered; the strain of the obtained molded article increases. Therefore, the reduced viscosity of the thermoplastic resin is preferably 1.50dL/g or less, more preferably 1.30dL/g or less, still more preferably 1.20dL/g or less, and particularly preferably 1.15dL/g or less.

The reduced viscosity of the thermoplastic resin is preferably 0.80dL/g or less, more preferably 0.75dL/g or less, and still more preferably 0.70dL/g or less, from the viewpoint of maintaining the minimum heat resistance, chemical resistance, abrasion resistance, and mechanical strength, and placing importance on moldability and strain suppression of a molded article.

The reduced viscosity of the thermoplastic resin is preferably 0.85dL/g or more, more preferably 0.90dL/g or more, and still more preferably 0.95dL/g or more, from the viewpoint of maintaining the lowest molding processability and attaching importance to heat resistance, chemical resistance, abrasion resistance, and mechanical strength.

The reduced viscosity of the thermoplastic resin is more specifically measured by the method described in the following example.

(method for producing thermoplastic resin)

The thermoplastic resin of the present disclosure can be produced using the compound (f) as a monomer. It is preferable to use monomers represented by the above formula (g), (h), (i), (j), (k), (l) or (m). Monomers other than these may also be used in combination. Examples of the other monomer include the other dihydroxy compound and the other dicarboxylic acid compound described above.

The thermoplastic resin of the present disclosure can be produced by a known production method for a thermoplastic resin having a carbonate bond or an ester bond, except that at least the compound (f) is used as a monomer.

The thermoplastic resin having a carbonate bond or an ester bond can be produced, for example, by a method of reacting a dihydroxy compound with a carbonate precursor substance (phosgene, a carbonic diester, etc.) or a method of reacting a dihydroxy compound with a dicarboxylic acid compound (a dicarboxylic acid or an ester-forming derivative thereof). Specific examples are shown below.

[ Process for producing polycarbonate ]

The method for producing a polycarbonate preferably includes a method of melt-polycondensing a dihydroxy compound and a carbonic acid diester (melt polymerization method).

In another interfacial polymerization method known as a method for producing a general polycarbonate, monomers that can be used are limited to aromatic dihydroxy compounds. The melt polymerization method can be applied to a wider range of structures including dihydroxy compounds having alcoholic hydroxyl groups. The interfacial polymerization method also requires the use of a highly toxic chlorine-containing solvent such as phosgene, methylene chloride, and chlorobenzene, and tends to have a high environmental load.

In the melt polymerization, a dicarboxylic acid compound may be used in combination.

The polycarbonate is a polymer having a structure in which structural units based on a dihydroxy compound are bonded to each other by carbonate bonds, and in the present invention, a part of the carbonate bonds are formed by a dicarboxylic acid structure (-O-C (═ O) -Q) ² Polyester carbonates substituted with — C (═ O) -O —), polyurethanes having a carbonate bond, and the like are also included in the polycarbonate.

In the above-mentioned method for producing a polycarbonate, a polyester carbonate is obtained by substituting a part of a carbonic diester with a dicarboxylic acid compound.

When only the dihydroxy compound and the carbonic acid diester are subjected to melt polycondensation, at least a part of the dihydroxy compound contains the structural unit (1). As the dihydroxy compound containing the structural unit (1), there may be mentioned the polymerization reactive group B in the above formula (f) ¹ And B ² A compound having a hydroxyl group (e.g., a compound represented by the above formula (f 1)).

As the dihydroxy compound, a dihydroxy compound having any one of the structural units (2) to (8) may be used in combination, or a dihydroxy compound other than these may be used in combination. Examples of the dihydroxy compound having any one of the structural units (2) to (8) include monomers represented by the above formulas (g), (h) or (i), and a polymerization reactive group J in the above formula (J) ¹ And J ² A monomer which is a hydroxyl-containing group, a polymerization-reactive group B in the above formula (m) ⁷ And J ⁸ A monomer that is a hydroxyl-containing group.

When the dihydroxy compound and the dicarboxylic acid compound are melt-polycondensed with the carbonic acid diester, at least a part of the dihydroxy compound may contain the structural unit (1), or at least a part of the dicarboxylic acid compound may contain the structural unit (1). As the dicarboxylic acid compound containing the structural unit (1), there may be mentioned the polymerization reactive group B in the above formula (f) ¹ And B ² Is a compound containing carboxyl group, ester group or hydroxyl ester group.

As the dicarboxylic acid compound, a dihydroxy compound having any one of the structural units (2) to (8) may be used in combination, or a dicarboxylic acid compound other than these may be used in combination.

Examples of the dicarboxylic acid compound having any of the structural units (2) to (8) include the polymerization reactive group J in the formula (J) ¹ And J ² A monomer having a carboxyl group or an ester group, a monomer represented by the formula (k) or (l), and a polymerizable group B in the formula (m) ⁷ And J ⁸ Is a monomer containing a carboxyl group or an ester group.

In using the polymerization-reactive group B in the above formula (f) ¹ And B ² The polymerization reactive group J in the formula (J) ¹ And J ² Or a polymerization reactive group B in the above formula (m) ⁷ And B ⁸ In the case of a monomer which is a hydroxy ester group, i.e., a hydroxy group having an ester skeleton, the polymerizable group B in the above formula (f) is used ¹ And B ² Or a polymerization reactive group B in the above formula (m) ⁷ And B ⁸ In the case of monomers containing hydroxyl-containing groups and carboxyl-containing groups, polyestercarbonates can also be obtained. Specific examples of the hydroxyl group having an ester skeleton include a 2-hydroxyethoxycarbonyl group and the like. In addition, as B ¹ And B ² 、B ⁷ And B ⁸ Specific examples of the hydroxyl-containing group and the carboxyl-containing group include hydroxyethoxy and ethoxycarbonyl; 2- (2-hydroxyethoxy) carbonyl with carboxyl; and so on.

[ Carbonic acid diester ]

Examples of the carbonic acid diester used in the melt polymerization method generally include those represented by the following formula (°). In the case of using the carbonic acid diester represented by formula (° O), either or both of the carbonate bond and the ester bond contain a carbonyl carbon (C (═ O)) derived from the carbonic acid diester.

[ solution 99]

Wherein E is ⁵ And E ⁶ Each independently represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having an optionally having a substituent, E ⁵ And E ⁶ May be the same or different.

Examples of the carbonic acid diester represented by the above formula (°) include diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, bis (chlorophenyl) carbonate, m-tolyl carbonate, dinaphthyl carbonate, and bis (biphenyl) carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among them, diaryl carbonates are preferred, and diphenyl carbonate is particularly preferred. These carbonic acid diesters may be used singly or in combination of two or more.

The molar ratio of the carbonic acid diester is preferably 0.90 to 1.10, more preferably 0.96 to 1.05, and still more preferably 0.98 to 1.03, based on the number of moles of all dihydroxy compounds used in the reaction.

In the case of using a dicarboxylic acid compound in combination, the molar ratio of the carbonic acid diester is preferably 0.90 to 1.10, more preferably 0.96 to 1.05, and further preferably 0.98 to 1.03, relative to the number of moles obtained by subtracting the number of moles of the total dicarboxylic acid compound from the number of moles of the total dihydroxy compound.

When the molar ratio is less than 0.90, the terminal hydroxyl groups of the produced polycarbonate increase, and the thermal stability of the polycarbonate may deteriorate or a desired high molecular weight material may not be obtained. If the molar ratio is more than 1.10, not only the rate of the transesterification reaction is decreased under the same conditions and it becomes difficult to produce a polycarbonate having a desired molecular weight, but also the amount of the residual carbonic acid diester in the produced polycarbonate increases and the residual carbonic acid diester volatilizes during molding and may cause defects.

[ polymerization catalyst ]

As a polymerization catalyst (transesterification catalyst) in the melt polymerization, a metal compound of group 1 and group 2 of the long periodic table of the elements can be mentioned. In addition to the metal compounds of group 1 and group 2 of the long-period periodic table, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in an auxiliary manner. Among them, it is particularly preferable to use only the metal compounds of group 1 and group 2 of the long period periodic table.

When the metal compounds of group 1 and group 2 of the long-period periodic table are used, the amount of the polymerization catalyst to be used is usually in the range of 0.1 to 100. mu. mol, preferably in the range of 0.5 to 50. mu. mol, and more preferably in the range of 1 to 25. mu. mol, in terms of metal, based on 1mol of the total dihydroxy compound used in the reaction. If the amount of the polymerization catalyst used is too small, it becomes difficult to obtain the polymerization activity required for producing a polycarbonate or a polyester carbonate having a desired molecular weight. On the other hand, if the amount of the polymerization catalyst used is too large, it may be difficult to produce a polycarbonate of the desired quality due to deterioration in color tone of the obtained polymer, generation of by-products, reduction in fluidity, increase in the amount of gel generated, and the like.

In addition, in the case of introducing a dicarboxylic acid structure, a titanium compound, a tin compound, a germanium compound, an antimony compound, a zirconium compound, a lead compound, an osmium compound or other ester exchange catalyst may be used in combination with or without the above-mentioned basic compound.

The amount of the transesterification catalyst to be used is usually in the range of 10. mu. mol to 1mmol, preferably 20. mu. mol to 800. mu. mol, and particularly preferably 50. mu. mol to 500. mu. mol, in terms of metal, based on 1mol of the total dihydroxy compound used in the reaction.

[ Metal content ]

When the polycarbonate or polyester carbonate contains a large amount of metal and metal ions, polymerization, coloring at the time of processing, and thermal decomposition may be easily caused. Therefore, it is preferable that the metal compound added as a catalyst falls within the above-mentioned appropriate range, and that metal components contaminating the raw materials, metals eluted from the reaction apparatus, and the like be reduced as much as possible. In particular, since the influence of Na, K, Cs and Fe is significant, the total content of Na, K, Cs and Fe in the polycarbonate or polyester carbonate is preferably 3 mass ppm or less.

The amount of the metal in the polycarbonate or polyester carbonate can be measured by a method such as atomic light emission, atomic light absorption, ICP, or the like after recovering the metal in the polycarbonate or polyester carbonate by wet ashing or the like.

[ polymerization method ]

In the production of a polycarbonate or a polyester carbonate by a melt polymerization method, a dihydroxy compound and, if necessary, a dicarboxylic acid compound are reacted with a carbonic diester in the presence of a polymerization catalyst. The polymerization is generally carried out by a multi-step process of two or more steps, and as for the polymerization reactor, it can be carried out by a process of two or more steps with changing the conditions using 1 reactor; it is also possible to carry out the reaction in two or more steps using 2 or more reactors and changing the respective conditions. From the viewpoint of production efficiency, the reaction is carried out using 2 or more, preferably 3 or more, further preferably 3 to 5, and particularly preferably 4 reactors. The polymerization reaction may be carried out in any of a batch type, a continuous type, and a combination of a batch type and a continuous type. From the viewpoint of production efficiency and quality stability, the continuous type is preferred.

In the melt polymerization reaction for obtaining a polycarbonate or a polyester carbonate, it is important to control the balance between the temperature and the pressure in the reaction system. If either of the temperature and the pressure is changed too rapidly, the unreacted monomer may be distilled out of the reaction system, and the molar ratio of the dihydroxy compound to the carbonic acid diester may be changed, whereby the desired polymer may not be obtained.

Specifically, in the reaction in the step 1, the reaction is carried out at a temperature of 130 to 250 ℃, preferably 140 to 240 ℃, more preferably 150 to 230 ℃ and at a pressure of 110 to 1kPa, preferably 70 to 3kPa, more preferably 30 to 5kPa (absolute pressure) as the maximum temperature of the internal temperature of the polymerization reactor, for 0.1 to 10 hours, preferably 0.5 to 3 hours, while distilling off the produced monohydroxy compound (in the case of diphenyl carbonate being used as the carbonic acid diester, the monohydroxy compound means phenol) to the outside of the reaction system.

After the 2 nd step, the pressure of the reaction system is gradually reduced from the pressure in the 1 st step, and then the produced monohydroxy compound is discharged to the outside of the reaction system, while the pressure (absolute pressure) of the reaction system is finally set to 5kPa or less, preferably 3kPa, and the maximum temperature of the internal temperature is set to 210 to 270 ℃, preferably 220 to 260 ℃, usually 0.1 to 10 hours, preferably 0.5 to 6 hours, and particularly preferably 1 to 3 hours.

In particular, in order to suppress coloration or thermal deterioration of the polycarbonate or polyester carbonate and obtain a polycarbonate or polyester carbonate having a good color tone and mechanical properties, the maximum temperature of the internal temperature in all reaction stages is preferably 270 ℃ or less, and particularly preferably 260 ℃ or less.

The reaction based on the interfacial polymerization method is generally a reaction of a dihydroxy compound with phosgene, which is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or amine compound such as pyridine is used. As the organic solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene is used. In addition, for the purpose of promoting the reaction, triethylamine, tetra-n-butylammonium bromide, for example, may be used

Tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds and the like. In this case, it is preferable to keep the reaction temperature at 0 to 40 ℃ usually, the reaction time at about 10 minutes to 5 hours, and the pH during the reaction at 9 or more.

When producing a polycarbonate or a polyester carbonate, a monofunctional hydroxyl compound generally used as a terminal terminator can be used in the polymerization reaction. In particular, in the case of a reaction using phosgene as a carbonate precursor, a monofunctional phenol is generally used as a terminal terminator for molecular weight adjustment, and the resulting polymer is capped with a group based on a monofunctional phenol. Therefore, the thermoplastic resin is excellent in thermal stability as compared with the case where phosgene is not used as a carbonate precursor substance.

[ Process for producing polyester ]

In the production of a polyester, for example, a dihydroxy compound and a dicarboxylic acid compound (dicarboxylic acid or an ester-forming derivative thereof) may be subjected to an esterification reaction or an ester exchange reaction, and the resulting reaction product may be subjected to a polycondensation reaction to produce a high molecular weight material having a desired molecular weight.

The proportion of ethylene glycol is preferably 0 to 50 mol% based on the total molar amount of all dihydroxy compounds. When the proportion of ethylene glycol is within the above range, the balance between heat resistance and moldability is excellent.

The polymerization method may be any suitable method selected from various methods such as a melt polymerization method such as a direct polymerization method and an ester exchange method, a solution polymerization method, and an interfacial polymerization method.

When the interfacial polymerization method is used, the following methods may be mentioned: the dicarboxylic acid chloride is dissolved in a water-immiscible organic solvent, the resulting solution (organic phase) is mixed with a basic aqueous solution (aqueous phase) containing an aromatic diol and a polymerization catalyst, and the polymerization reaction is carried out while stirring at a temperature of 50 ℃ or lower, preferably 25 ℃ or lower, for 0.5 to 8 hours.

As the solvent used in the organic phase, a solvent which is incompatible with water but dissolves the polyester is preferable. Examples thereof include chlorine-based solvents such as methylene chloride, 1, 2-dichloroethane, chloroform and chlorobenzene; aromatic hydrocarbon solvents such as toluene, benzene and xylene. Methylene chloride is preferred because it is easy to use it in production.

Examples of the alkaline aqueous solution used in the aqueous phase include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, and the like.

When the melt polymerization method is used, it is generally preferred to mix the dihydroxy compound with the dicarboxylic acid or its diester and to carry out the reaction at a temperature of usually 120 to 350 ℃, preferably 150 to 300 ℃, and more preferably 180 to 270 ℃. The degree of vacuum is varied stepwise to a final level of 0.13kPa or less, and the resultant water, alcohol, or other hydroxyl compound is distilled off to the outside of the system, usually for a reaction time of about 1 to 10 hours.

In order to increase the polymerization rate in the melt polymerization method, a transesterification catalyst or a polymerization catalyst may be used.

The transesterification catalyst is not particularly limited, and various transesterification catalysts can be used. Examples thereof include compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, and lead. Specifically, oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like containing these elements are mentioned. Among them, compounds such as oxides, acetates and alcoholates of manganese, magnesium, zinc, titanium and cobalt are preferable from the viewpoint of melt stability, color tone and less insoluble foreign matter in the polymer of the thermoplastic resin. These transesterification catalysts may be used singly or in combination of two or more.

The polymerization catalyst is not particularly limited, and various polymerization catalysts can be used. Examples thereof include antimony compounds, titanium compounds, germanium compounds, tin compounds and aluminum compounds. Examples of such compounds include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like of antimony, titanium, germanium, tin and aluminum. These compounds may be used alone or in combination of two or more.

Among them, tin compounds, titanium compounds and germanium compounds are preferable from the viewpoint of melt stability and color tone of the thermoplastic resin.

The amount of the catalyst to be used is, for example, preferably 1X 10 based on 1 mole of the dicarboxylic acid compound based on the total amount of the transesterification catalyst and the polymerization catalyst ^-8 ～1×10 ^-3 The molar range.

In the production of polyesters, an end-capping agent may be used for the purpose of adjusting the molecular weight and improving the thermal stability. Examples of the blocking agent include monofunctional hydroxyl compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, and ketene imine compounds.

The thermoplastic resin of the present disclosure may contain a copolymerization component other than the dihydroxy compound and the dicarboxylic acid compound.

(additives)

The thermoplastic resin composition of the present disclosure may be prepared by adding additives such as a heat stabilizer, an antioxidant, a mold release agent, a plasticizer, a filler, and an ultraviolet absorber as needed.

As the release agent, a release agent containing an ester of an alcohol and a fatty acid is preferable. The proportion of the ester is preferably 90% by mass or more, more preferably 95% by mass or more, relative to the total mass of the release agent.

Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial ester or a full ester of a polyhydric alcohol and a fatty acid. The ester of a monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or full ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Among them, stearyl stearate is preferable.

Examples of partial esters or full esters of polyhydric alcohols and saturated fatty acids include partial esters or full esters of dipentaerythritol such as stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monobehenate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl diphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferable.

The content of the release agent in the thermoplastic resin composition is preferably 0.005 to 2.0 parts by mass, more preferably 0.01 to 0.6 parts by mass, and still more preferably 0.02 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

Examples of the heat stabilizer include a phosphorus-based heat stabilizer, a sulfur-based heat stabilizer, and a hindered phenol-based heat stabilizer.

Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples thereof include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite, monodecyldiphenyl phosphite, monooctyldiphenyl phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, tris (2, 4-dicumylphenyl) pentaerythritol diphosphite, and the like, Bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-ortho-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2, 4-di-tert-butylphenyl) -4,4 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4,3 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3,3 ' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like.

Of these, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4,4 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4,3 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3,3 ' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl phosphonite are preferred, and tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphonite.

The content of the phosphorus-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 part by mass per 100 parts by mass of the thermoplastic resin.

Examples of the sulfur-based heat stabilizer include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), dilauryl-3, 3 ' -thiodipropionate, dimyristyl-3, 3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate, and the like. Among them, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3, 3 '-thiodipropionate and dimyristyl-3, 3' -thiodipropionate are preferable, and pentaerythritol-tetrakis (3-laurylthiopropionate) is particularly preferable.

The content of the sulfur-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by mass per 100 parts by mass of the thermoplastic resin.

Examples of the hindered phenol-based heat stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 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-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3, 9-bis {1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5,5) undecane, and the like. Among them, octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate and pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] are preferable.

The content of the hindered phenol-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.3 part by mass per 100 parts by mass of the thermoplastic resin.

The phosphorus-based heat stabilizer and the hindered phenol-based heat stabilizer may be used in combination.

The ultraviolet absorber is preferably at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imino ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], and the like.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2' -carboxybenzophenone.

Examples of the triazine-based ultraviolet absorber include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5- [ (octyl) oxy ] -phenol, and the like.

Examples of the cyclic imino ester-based ultraviolet absorber include 2, 2' -p-phenylenebis (3, 1-benzoxazin-4-one).

Examples of the cyanoacrylate-based ultraviolet absorber include 1, 3-bis- [ (2 ' -cyano-3 ', 3 ' -diphenylacryloyl) oxy ] -2, 2-bis [ (2-cyano-3, 3-diphenylacryloyl) oxy ] methyl) propane, 1, 3-bis- [ (2-cyano-3, 3-diphenylacryloyl) oxy ] benzene, and the like.

The content of the ultraviolet absorber in the thermoplastic resin composition is preferably 0.01 to 3.0 parts by mass per 100 parts by mass of the thermoplastic resin. When the content of the ultraviolet absorber is within the above range, sufficient weather resistance can be imparted to a molded article of the thermoplastic resin composition depending on the application.

(blending with other thermoplastic resins)

The thermoplastic resins of the present disclosure may be blended with other thermoplastic resins. For the reason that the optical properties are good and injection molding tends to be possible, it is preferable to coexist other thermoplastic resins. Specific examples of the other thermoplastic resin to be coexistent include a polycondensation polymer, an olefin polymer, and an addition polymerization polymer, and a polycondensation polymer is preferable.

Examples of the polycondensation polymer include polycarbonate, polyester, polyamide, polyestercarbonate, polyamide, polyimide, and the like. Among them, polyester and polycarbonate are preferable.

For example, polycarbonate, polyester, and polyester carbonate obtained by using one or more of bisphenol a, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis (6-hydroxy-2-naphthyl) fluorene, dinaphthol, 2 '-bis (2-hydroxyethoxy) -1, 1' -Binaphthyl (BNEO), and 9, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl ] fluorene (BNEF) are preferably used. These polycarbonates, polyesters and polyester carbonates may be used singly or in combination of two or more.

In the case of molding the thermoplastic resin of the present disclosure, since it preferably has optical transparency, the other thermoplastic resin blended with the thermoplastic resin of the present disclosure preferably has compatibility with the thermoplastic resin of the present disclosure.

(use)

The thermoplastic resin of the present disclosure can be used in optical members such as optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, light guide plates, and the like.

< lens >

The thermoplastic resin of the present disclosure is suitable for optical members, particularly lenses.

In a preferred embodiment, the lens is an aspherical lens. Since the spherical aberration can be substantially zero by using 1 lens, it is not necessary to use a combination of 2 or more spherical lenses to eliminate the spherical aberration, and the weight and molding cost can be reduced. Therefore, among the lenses, an aspherical lens is particularly useful as a camera lens.

In another preferred embodiment, the lens is a meniscus lens with one convex side and one concave side.

The thermoplastic resin of the present disclosure has high molding flowability, and is therefore particularly useful as a material for a thin, small and complex-shaped lens. The thickness of the central portion is 0.05 to 3.0mm, preferably 0.05 to 2.0mm, and more preferably 0.1 to 2.0mm, as a specific lens size. The diameter is 1.0mm to 20.0mm, more preferably 1.0mm to 10.0mm, and still more preferably 3.0mm to 10.0 mm.

Lenses formed from the thermoplastic resins of the present disclosure are molded by any method such as die molding, cutting, grinding, laser machining, electrical discharge machining, etching, and the like. Among them, mold molding is more preferable from the viewpoint of production cost. Examples of the mold forming include injection molding, extrusion molding, compression molding, casting, roll processing, and the like.

When a lens formed of the thermoplastic resin of the present disclosure is produced by injection molding, the molding is preferably performed at a cylinder temperature of 230 to 350 ℃ and a mold temperature of 70 to 170 ℃, and more preferably at a cylinder temperature of 250 to 300 ℃ and a mold temperature of 80 to 160 ℃. When the cylinder temperature is 350 ℃ or lower, the thermoplastic resin is not easily decomposed and colored, and when the cylinder temperature is 230 ℃ or higher, the melt viscosity is low, and molding is easy. When the mold temperature is 170 ℃ or lower, the molded piece made of the thermoplastic resin can be easily taken out from the mold. If the mold temperature is 70 ℃ or higher, rapid solidification of the thermoplastic resin in the mold during molding can be suppressed, and the shape of the molded piece can be easily controlled. In addition, the molding imparted to the mold is easily transferred sufficiently.

The present disclosure further includes the following aspects [1] to [5 ].

[1] A compound represented by the following formula (f 1).

[ solution 100]

Wherein L is ¹ And L ² Independently represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 4 to 10 carbon atoms, or an aralkylene group having 6 to 12 carbon atoms, wherein m represents an integer of 1 to 4, n represents an integer of 1 to 4,

(L ¹ O) _m bonded to any one of carbon atoms of substitution position numbers 1-6, (L) ² O) _n Bonded to any one of the carbon atoms of substitution position numbers 8 to 13, and unbonded (L) in the carbon atoms of substitution position numbers 1 to 6,8 to 13 ¹ O) _m Or (L) ² O) _n Carbon atom of (2)Each of which is independently bonded with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and having or not having a substituent, an aryl group having 3 to 14 carbon atoms and having or not having a substituent, an acyl group having 1 to 10 carbon atoms and having or not having a substituent, an alkoxy group having 1 to 10 carbon atoms and having or not having a substituent, an aryloxy group having 3 to 14 carbon atoms and having or not having a substituent, an acyloxy group having 1 to 10 carbon atoms and having or not having a substituent, an amino group having or not having a substituent, an alkenyl group having 2 to 10 carbon atoms and having or not having a substituent, an alkynyl group having 2 to 10 carbon atoms and having or not having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group.

[2] The compound according to the above [1], wherein m and n in the above formula (f1) represent 1.

[3]As described above [1]Or [2]]Wherein m and n in the formula (f1) represent 1, and the carbon atoms at the substitution positions are numbered 1 to 6 and 8 to 13, and are not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

[4]As described above [1]～[3]The compound according to any one of the above formulae (f1), wherein L is represented by the formula ¹ And L ² Independently represents an alkylene group having 1 to 10 carbon atoms with or without a substituent, m and n represent 1, and the unbonded HO (L) in the carbon atoms of the substitution position numbers 1 to 6 and 8 to 13 ¹ O) _m Or HO (L) ² O) _n To which a hydrogen atom is bonded.

[5] A thermoplastic resin, comprising: a structure in which 2 or more 2-valent structural units are linked via a 2-valent linking group,

at least a part of the 2 or more valent-2 structural units is a structural unit represented by the following formula (1),

at least a part of the 2-valent linking group is a carbonate bond or an ester bond.

[ solution 101]

(L ¹ O) _m bonded to any one of carbon atoms of substitution position numbers 1-6, (L) ² O) _n Bonded to any one of the carbon atoms of substitution position numbers 8 to 13, and unbonded (L) in the carbon atoms of substitution position numbers 1 to 6,8 to 13 ¹ O) _m Or (L) ² O) _n The carbon atom of (A) is independently bonded with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and having or not having a substituent, an aryl group having 3 to 14 carbon atoms and having or not having a substituent, an acyl group having 1 to 10 carbon atoms and having or not having a substituent, an alkoxy group having 1 to 10 carbon atoms and having or not having a substituent, an aryloxy group having 3 to 14 carbon atoms and having or not having a substituent, an acyloxy group having 1 to 10 carbon atoms and having or not having a substituent, an amino group having or not having a substituent, an alkenyl group having 2 to 10 carbon atoms and having or not having a substituent, an alkynyl group having 2 to 10 carbon atoms and having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group.

Examples

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the case where no specific description is given, "%" represents "% by mass".

< description of abbreviation >

The meanings of the abbreviations in the following description are as follows. The chemical structures of 2,12DNF, 2,12DNFE, 2,12DNFM, and 3,11DNFE are shown in synthesis examples 1 to 4 described later.

2,12DNFE:2, 12-bis (2-hydroxyethoxy) dinaphthofuran.

2,12DNF:2, 12-dihydroxydinaphthofuran.

3,11 DNFE: 3, 11-bis (2-hydroxyethoxy) dinaphthofuran.

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

BNEO: 2,2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl.

BNEF: 9, 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene.

EG: ethylene glycol.

2, 12-DHEDNT: 2, 12-bis (2-hydroxyethoxy) dinaphthothiophene.

BPA: bisphenol A.

DPC: diphenyl carbonate.

PFM: bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl ] methane.

DMT: dimethyl terephthalate.

2,12 DNFM: 2, 12-bis (carboxymethoxy) dinaphthol [2,1-b:1 ', 2' -d ] furan.

3,11 DNF: 3, 11-dihydroxydinaphthofuran.

6,8 DNF: 6, 8-dihydroxydinaphthofuran.

TBT: titanium tetrabutoxide.

< measuring method >

The methods for measuring the glass transition temperature Tg, refractive index, abbe number vd, reduced viscosity, and NMR of the polycarbonate copolymer (thermoplastic resin) of each example are as follows.

(Tg)

About 10mg of the sample was measured by heating at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter ("EXSTAR 6220" manufactured by SII Nanotechnology Co., Ltd.), and the glass transition initiation temperature at the midpoint was determined from the temperature at which a straight line (the straight line is a straight line extending from the base line on the low temperature side and the base line on the high temperature side in the longitudinal direction at an equal distance) intersects with the curve of the stepwise change part of the glass transition in accordance with JIS K7121 (1987) and the value was defined as Tg.

(refractive index, Abbe number)

The sample was press-molded at 200 to 250 ℃ to prepare a film having a thickness of about 200 μm, and the obtained film was cut into a long piece having a width of about 8mm and a length of 10 to 20mm to prepare a measurement test piece.

For the measurement test piece, nC, nD, ne, and nF as refractive indices at respective wavelengths were measured using an interference filter having wavelengths of 656nm (C line), 589nm (D line), 546nm (e line), and 486nm (F line) by an abbe refractometer ("DR-M4" manufactured by agago corporation). In the measurement, diiodomethane or 1-bromonaphthalene was used as an interfacial solution, and the measurement was performed at 20 ℃.

The Abbe number vd is calculated from the measurement result by the following equation. The larger the abbe number is, the smaller the wavelength dependence of the refractive index is, and for example, the smaller the deviation of the focal point due to the wavelength when a single lens is produced is.

νD＝(1-nD)/(nC-nF)

(reduced viscosity)

As the solvent, a 1:1 mixed solvent (mass ratio) of phenol and 1,1,2, 2-tetrachloroethane was used to prepare a solution of a sample, and the solution and the solvent were measured by a Ubbelohde viscometer using a DT-504 type automatic viscometer manufactured by central processing at a temperature of 30.0 ℃. + -. 0.1 ℃. The concentration of the solution was adjusted to 1.00g/dl with precision. The sample was dissolved for 30 minutes while being stirred at 110 ℃ and then cooled for measurement. According to the transit time t of the solvent ₀ The solution passage time t was determined by the following equation _rel 。

η _rel ＝t/t ₀ (g·cm ^-1 ·sec ^-1 )

According to the relative viscosity eta _rel The specific viscosity η was obtained by the following equation _sp 。

η _sp ＝(η-η ₀ )/η ₀ ＝η _rel -1

Specific viscosity η _sp The reduced viscosity (. eta.) is obtained by dividing the concentration c (g/dl) by the following equation _red . The higher the value, the larger the molecular weight.

η _red ＝η _sp /c

(NMR)

About 30mg of a sample was put into an NMR sample tube having an outer diameter of 5mm, and dissolved in 0.7ml of deuterated chloroform (containing 0.03 v/v% tetramethylsilane). The resonance frequency was 950.3MHz, and the resonance frequency was inverted using "AVANCE III 950" manufactured by Bruker corporationAngle 30 DEG, measurement temperature 25 DEG ¹ H-NMR。

(coefficient of photoelasticity)

About 4g of each resin example vacuum-dried at 80 ℃ for 5 hours was subjected to hot pressing at a hot pressing temperature of 200 to 250 ℃, preheating for 1 to 3 minutes, and a pressure of 20MPa for 1 minute by using a spacer having a width of 8cm, a length of 8cm, and a thickness of 0.5mm, and then taken out together with the spacer, and subjected to pressure cooling at a pressure of 20MPa for 3 minutes by a water-tube cooling press to prepare a sheet. A sample having a width of 5mm and a length of 20mm was cut out from the film.

A birefringence measurement device comprising a He-Ne laser, a polarizer, a compensation plate, an analyzer and a photodetector was combined with a vibration-type viscoelasticity measurement device ("DVE-3" manufactured by Rheology corporation) to prepare a measurement device (for details, refer to Vol.19, p93-97(1991) of Rheology society, Japan).

The cut sample was fixed to a viscoelasticity measuring apparatus, and the storage modulus E' was measured at a frequency of 96Hz at room temperature of 25 ℃. At the same time, the emitted laser beam is sequentially passed through a polarizing element, a sample, a compensation plate, and an analyzer, picked up by a photodetector (photodiode), passed through a lock-in amplifier, and a phase difference with respect to the amplitude and strain of the waveform of the angular frequency ω or 2 ω is obtained, thereby obtaining a strain optical coefficient O'. At this time, the polarizing element and the analyzer are oriented orthogonally to each other and are each at an angle of π/4 to the elongation direction of the sample. The photoelastic coefficient C was obtained from the following equation using the storage modulus E 'and the strain optical coefficient O'.

C＝O’/E’

< Synthesis of Dinaphthofuran Compound >

Synthetic example 1: synthesis of 2,12DNF

Synthesis of (1-1) (1,1 ' -binaphthyl) -2,2 ', 7,7 ' -tetraol

2, 7-dihydroxynaphthalene (80g, 499.5mol), ferric chloride (162.0g, 998.9mol), water (2.0L) and isopropanol (300mL) were added to the flask, and the mixture was stirred at 40 ℃ for 3 hours. After the reaction mixture was cooled to room temperature, ethyl acetate (600mL) and water (600mL) were added to extract the organic layer. The reaction mixture was concentrated and purified by silica column chromatography to obtain 54.2g (yield: 67.8%, HPLC purity: 89%) of (1,1 ' -binaphthyl) -2,2 ', 7,7 ' -tetraol as a green solid.

¹ H NMR：(500MHz,DMSO-d ₆ )δppm＝9.20(s,2H),8.93(s,2H),7.68(dd,J＝8.5,6.5Hz,4H),7.07(d,J＝9.0Hz,2H),6.78(dd,J＝8.5,2.5Hz,2H),6.29(d,J＝2.0Hz,2H).

[ solution 102]

Synthesis of (1-2) (1,1 ' -binaphthyl) -2,2 ' -diol-7, 7 ' -dimethoxy

To a flask were added (1,1 ' -binaphthyl) -2,2 ', 7,7 ' -tetraol (160g, 502.6mol), methanol (1800mL), and sulfuric acid (345.1g, 3.52mol), and the mixture was stirred at 80 ℃. Ethyl acetate (2L) was added to the reaction solution at room temperature, and the pH was neutralized to 7-8 with a saturated aqueous potassium carbonate solution. Water (2L) was added to extract the organic layer, and the mixture was concentrated to obtain 417g of (1,1 ' -binaphthyl) -2,2 ' -diol-7, 7 ' -dimethoxy as a brown liquid. A portion of the monomethoxy matrix is also obtained, which is used directly in the next process.

¹ H NMR：(400MHz,CDCl ₃ )δppm＝7.89-7.82(m,2H),7.80-7.73(m,2H),7.24-7.18(m,2H),7.06-6.97(m,2H),6.49(br s,2H),5.08(br s,2H),3.74-3.42(s,6H).

[ solution 103]

(1-3) Synthesis of 2, 12-Dimethoxydinaphthofuran

To a flask were added (1,1 ' -binaphthyl) -2,2 ' -diol-7, 7 ' -dimethoxy (180g, 446.9mol), p-toluenesulfonic acid (115.4g, 670.4mol), toluene (2.4L), and stirred at 140 ℃ for three days. After concentrating the reaction solution, diluting the reaction solution by using ethyl acetate (8L), and neutralizing the reaction solution to the pH of 7-8 by using a saturated potassium carbonate aqueous solution. Thereafter, water (8L) was added to extract an organic layer, and the mixture was purified by silica column chromatography to obtain 117g (HPLC purity: 64%) of 2, 12-dimethoxydinaphthofuran as a yellow solid.

[ solution 104]

(1-4) Synthesis of 2,12DNF

2, 12-Dimethoxydinaphthofuran (48.9g, 148.9mol) and methylene chloride (1,0L) were charged into a flask, and boron tribromide (93.3g, 372.3mol) was added at-78 ℃ and stirred at 20 ℃ for 5 hours. Water (3L) was added dropwise, and the mixture was concentrated to remove the organic layer, and then ethyl acetate (3L) was added to extract the organic layer. Concentration gave 43g of 2,12DNF as a white solid (yield: 96.2%, HPLC purity: 100%).

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝10.07(s,2H),8.31(d,J＝1.6Hz,2H),8.01(d,J＝8.8Hz,2H),7.95(d,J＝8.8Hz,2H),7.71(d,J＝8.8Hz,2H),7.19(dd,J＝8.8,2.0Hz,2H).

[ solution 105]

[ Synthesis example 2: synthesis of 2,12DNFE ]

2,12DNF (7g, 23.3mol), dimethylformamide (230mL), and potassium carbonate (322.2mg, 2.33mol) were charged into a flask, and ethylene carbonate (8.2g, 93.2mol) was dissolved in dimethylformamide (20mL) and then added dropwise to the flask. After the reaction mixture was stirred at 120 ℃ for 16 hours, ice water (400mL) was added and the mixture was filtered to obtain a solid. This solid was subjected to suspension washing with acetonitrile at 20 ℃ to obtain 2,12DNFE8.5g (yield: 94.3%, HPLC purity: 100%) as a gray solid.

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝8.43(d,J＝2.0Hz,2H),8.13(d,J＝8.8Hz,2H),8.04(d,J＝8.8Hz,2H),7.82(2H,d,J＝8.8Hz),7.36(dd,J＝8.8,2.0Hz,2H),4.97(t,J＝5.2Hz,2H),4.28(t,J＝4.8Hz,4H),3.86(dd,J＝8.8,5.2Hz,4H).

[ solution 106]

[ Synthesis example 3: synthesis of 2,12DNFM

The flask was charged with 2,12DNF (15g, 49.95mmol), acetonitrile (1.5L), K ₂ CO ₃ (27.61g, 199.80mmol) and methyl 2-bromoacetate (19.10g, 124.87mmol, 11.79mL) were stirred at 85 ℃ under nitrogen for 16 hours.

The reaction mixture was filtered at 80 ℃ and the filtered solid was dried under vacuum to give a solid (23 g). Next, the obtained solid and acetonitrile (200mL) were added to the flask, stirred at 80 ℃ for 1 hour, and cooled at 20 ℃ for 1 hour. Thereafter, the solution was filtered, and the filtered solid was dried to obtain 20.6g of 2,12DNFM as a white solid (yield: 93%, HPLC purity: 99.4%).

¹ H NMR：(400MHz,CDCl ₃ )δppm＝8.56(d,J＝2.0Hz,2H),8.01(d,J＝8.8Hz,2H),7.89(d,J＝8.8Hz,2H),7.71(d,J＝8.8Hz,2H),7.29(dd,J＝2.0,8.8Hz,2H),4.94(s,4H),3.81(s,6H).

[ solution 107]

[ Synthesis example 4: synthesis of 3,11DNFE ]

(3-1) Synthesis of 2-hydroxy-6-methoxy-naphthalene

Dioxane (1000mL) and H were added to the flask ₂ O (200mL) and 2-bromo-6-methoxy-naphthalene (100g, 421.78mmol, 250.00mL) were degassed and replaced with hydrogen by repeating the procedure 3 times. Followed by addition of KOH (94.66g, 1.69mol), t-BuXphos (7.16g, 16.87mmol) and Pd ₂ (dba) ₃ (5g, 5.46mmol), the degassing and hydrogen substitution was repeated 3 times, followed by stirring at 80 ℃ for 16 hours. The reaction mixture was washed with ethyl acetate (1)000 mL. times.4), followed by extraction of the organic layer with H ₂ O (1000 mL. times.2) was washed, filtered, and the filtrate was concentrated under reduced pressure to give a crude product. Thereafter, the crude product and dichloromethane were added to the flask: n-heptane (120 mL: 1200mL), stirred at 25 ℃ for 60 minutes, collected the solid by filtration and dried under vacuum to give 55g (yield: 55%) of 2-hydroxy-6-methoxy-naphthalene as a yellow solid.

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝7.64-7.59(m,1H),7.56(d,J＝9.2Hz,1H),7.17(d,J＝2.4Hz,1H),7.08-7.00(m,3H),3.81(s,3H).

[ solution 108]

Synthesis of (3-2)1- (2-hydroxy-6-methoxy-1-naphthyl) -6-methoxy-naphthalen-2-ol

To the flask was added isopropanol (195mL), 2-hydroxy-6-methoxy-naphthalene (55g, 315.74mmol), H ₂ O(1270mL)、FeCl ₃ (102.43g, 631.47mmol, 36.58mL), and stirred at 40 ℃ for 3 hours under nitrogen. The reaction mixture was extracted with ethyl acetate (1000X 2) and washed with H ₂ O (1000 mL. times.2) and saturated brine (1000mL) were washed, filtered, and the filtrate was concentrated under reduced pressure to give 1- (2-hydroxy-6-methoxy-1-naphthyl) -6-methoxy-naphthalen-2-ol (24g, yield: 43%).

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝8.95(s,2H),7.74(d,J＝8.0Hz,2H),7.26(s,4H),6.85(s,4H),3.81(s,6H).

[ solution 109]

(3-3) Synthesis of 3, 11-Dimethoxydinaphthofuran

A stirred mixture of 1- (2-hydroxy-6-methoxy-1-naphthyl) -6-methoxy-naphthalen-2-ol (51g, 147.24mmol) in toluene (1000mL) was stirred with p-TsOH (50.71g, 294.48mmol) under nitrogen at 125 deg.CFor 28 hours. The reaction mixture was cooled to 25 ℃ with K ₂ CO ₃ The solution was diluted with a saturated aqueous solution (about 1000mL), the pH was adjusted to 6-7, and the precipitated solid was obtained by filtration. The obtained solid and dioxane (1500mL) were added to a flask, and stirred at 105 ℃ for 2 hours, followed by addition of ethyl acetate (300mL) and n-heptane (1500mL), and after stirring at 25 ℃ for 2 hours, filtration was performed, whereby 26g of 3, 11-dimethoxydinaphthofuran was obtained as a gray solid (yield: 50%).

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝8.95(d,J＝9.2Hz,2H),8.06-8.00(m,2H),7.99-7.91(m,2H),7.66(d,J＝2.8Hz,2H),7.48(dd,J＝2.8,9.2Hz,2H),3.95(s,6H).

[ solution 110]

(3-4) Synthesis of 3, 11-dihydroxydinaphthofuran

Into the flask were added 3, 11-dimethoxydinaphthofuran (34g, 103.54mmol), CH ₂ Cl ₂ (600mL), cooled to-78 ℃ under nitrogen, and BBr added dropwise ₃ (77.82g, 310.63mmol, 29.93 mL). After stirring for 16 hours at 25 ℃ H was added ₂ O (500mL), extracted with ethyl acetate (500 mL. times.3). The obtained organic layer was washed with saturated brine (500mL), filtered and concentrated to obtain a solid, and the obtained solid was added to ethyl acetate (60mL) and n-heptane (600mL) in a flask, stirred at 25 ℃ for 16 hours and filtered to obtain a solid, which was then subjected to 2 times of this operation to obtain 3, 11-dihydroxydinaphthofuran (30g, yield: 75%) as a brown solid.

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝9.93(s,2H),8.89(d,J＝9.2Hz,2H),7.90-7.83(s,4H),7.44-7.37(m,4H).

[ solution 111]

(3-5) Synthesis of 3,11DNFE

Into a flask was added 3, 11-dihydroxydinaphthofuran (10g, 33.30mmol), DMF (200mL), K ₂ CO ₃ (460.22mg, 3.33mmol), and after keeping it under nitrogen, ethylene carbonate (11.73g, 133.20mmol, 8.89) mL) was further dissolved in DMF (120mL) to prepare a solution, which was added dropwise at 120 ℃. After stirring at 120 ℃ for 16 hours, water (500mL) was injected and the precipitated solid was obtained by filtration and dried to give a solid. The obtained solid and methanol (1500mL) were added to the flask, stirred at 80 ℃ for 2 hours, and filtered to obtain a solid, and this operation was repeated 3 times.

Subsequently, the obtained solid and acetonitrile (100mL) were added to the flask, stirred at 80 ℃ for 16 hours, and filtered to obtain a solid. Subsequently, the obtained solid and toluene (100mL) were added to the flask, and the mixture was stirred at 120 ℃ for 2 hours, and after filtration, the solid was obtained, and this operation was performed 3 times. Vacuum drying was carried out to obtain 3,11DNFE as a pale yellow crystalline solid (5.9g, yield: 72%).

¹ H NMR：(400MHz,DMSO-d ₆ )δppm＝8.96(d,J＝9.2Hz,2H),8.05-7.94(m,4H),7.67(d,J＝2.8Hz,2H),7.50(dd,J＝9.2,2.8Hz,2H),4.97(t,J＝5.6Hz,2H),4.20(t,J＝5.2Hz,4H),3.84(q,J＝5.2Hz,4H).

[ solution 112]

< production of thermoplastic resin >

(use of raw materials)

Except for the above-produced dinaphthofuran compound, the raw materials used for producing the polycarbonate copolymer in the following examples and comparative examples were as follows.

And BPEF: product of OSAKA GAS CHEMICALS company.

BNEO: synthesized by the method disclosed in Japanese patent laid-open publication No. 2016-204293.

BNEF: synthesized by the method disclosed in international publication No. 2018/230394.

EG: fuji film and guko products.

BPA: mitsubishi chemical engineering plastics corporation.

DPC: product of Mitsubishi chemical company.

PFM: synthesized by the method disclosed in Japanese patent laid-open publication No. 2015-25111.

DMT: fuji film and guko products.

Cesium carbonate (Cs) ₂ CO ₃ Fuji film and products of mitsunka).

Calcium acetate monohydrate (Ca (CH) ₃ COO) ₂ ·H ₂ O, product of Kishida Chemical).

(example 1)

1.27g (0.0033 mol) of 2,12DNFE, 12.88g (0.0294 mol) of BPEF, 7.13g (0.0333 mol) of DPC, and 5.75X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-4 g(3.26×10 ^-6 Mole) was put into a reaction vessel as a 0.2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and the temperature was raised to 220 ℃ over 60 minutes under normal pressure with stirring as necessary to dissolve the raw materials.

In the step 1 of the reaction, the pressure was reduced from normal pressure to 13.3kPa for 40 minutes while maintaining 220 ℃ and then maintained at 13.3kPa for 60 minutes, and the produced phenol was discharged to the outside of the reaction vessel. In the 2 nd step, the temperature of the heating tank was raised to 240 ℃ over 20 minutes, and the pressure was controlled to 0.200kPa or less over 30 minutes, and the produced phenol was discharged out of the reaction vessel. After the stirring torque reached a predetermined value, the reaction was terminated, and the resulting reaction product was taken out of the reaction vessel to obtain a polycarbonate copolymer.

The reduced viscosity of the resulting polycarbonate copolymer was 0.158 dl/g. When the refractive index was measured at 20 ℃, nC-1.639, nD-1.647, ne-1.655, nF-1.669 and abbe number 22. The NMR spectrum of the polycarbonate copolymer is shown in fig. 5.

(example 2)

3.89g (0.0100 mol) of 2,12DNFE, 10.24g (0.0234 mol) of BPEF, 7.44g (0.0347 mol) of DPC, and 2.94X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-3 g(1.67×10 ^-5 Moles) was charged into a reaction vessel as a 2% aqueous solution, and the raw materials were dissolved by heating the vessel to 150 ℃ under a nitrogen atmosphere, stirring if necessary, and raising the temperature to 220 ℃ over 60 minutes under normal pressure, to obtain a polycarbonate copolymer in the same manner as in example 1.

The reduced viscosity of the polycarbonate copolymer obtained was 0.247 dl/g.

(example 3)

3.36g (0.0087 mol) of 2,12DNFE, 10.89g (0.0202 mol) of BNEF, 6.43g (0.0300 mol) of DPC, and 2.54X 10 of calcium acetate monohydrate as a catalyst ^-4 g(1.44×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and the raw materials were dissolved by heating the vessel to 150 ℃ under a nitrogen atmosphere, stirring the vessel if necessary, and raising the temperature to 220 ℃ under normal pressure for 60 minutes, to obtain a polycarbonate copolymer in the same manner as in example 1.

The reduced viscosity of the polycarbonate copolymer thus obtained was 0.429 dl/g.

(example 4)

1.07g (0.0028 mol) of 2,12DNFE, 10.87g (0.0248 mol) of BPEF, 4.84g (0.0226 mol) of DPC, 3.53g (0.0055 mol) of PFM, and 3.30X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-3 g(1.87×10 ^-5 Mole) was put into a reaction vessel as a 2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and stirred as necessary, and the temperature was raised to 180 ℃ under normal pressure for 60 minutes to dissolve the raw materials. The temperature was further raised to 250 ℃ over 120 minutes, and the reaction mixture was held at 250 ℃ for 30 minutes to carry out the first reaction.

As the second reaction, while controlling the temperature from 250 ℃ to 270 ℃ over 90 minutes and the pressure from the atmospheric pressure to 0.200kPa or less over 90 minutes, the pressure was gradually reduced, and the produced phenol was discharged to the outside of the reaction vessel. After reaching a predetermined stirring torque, the reaction was terminated, and the resultant reaction product was taken out from the reaction vessel to obtain a polyester carbonate copolymer.

The reduced viscosity of the resulting polycarbonate copolymer was 0.334 dl/g.

(example 5)

4.41g (0.0114 mol) of 2,12DNFE, 2.68g (0.0061 mol) of BPEF, 11.20g (0.0175 mol) of PFM, and 3.30X 10 of calcium acetate monohydrate as a catalyst ^-3 g(1.87×10 ^-5 Mole) was put into a reaction vessel as a 2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and stirred as necessary, and the temperature was raised to 180 ℃ under normal pressure for 60 minutes to dissolve the raw materials. The temperature was further raised to 250 ℃ over 120 minutes, and the reaction mixture was held at 250 ℃ for 30 minutes to carry out the first reaction.

As the second reaction, the pressure was reduced while controlling the temperature from 250 ℃ to 270 ℃ over 90 minutes and the pressure from the atmospheric pressure to 90 minutes so that the pressure was gradually reduced to 0.200kPa or less, and the produced phenol was discharged to the outside of the reaction vessel. After the reaction was completed with a predetermined stirring torque, the resultant reaction product was taken out from the reaction vessel to obtain a polyester copolymer.

The reduced viscosity of the resulting polyester copolymer was 0.390 dl/g.

(example 6)

7.23g (0.0186 mol) of 2,12DNFE, 3.34g (0.0062 mol) of BNEF, 2.70g (0.0435 mol) of EG, 6.03g (0.0310 mol) of DMT and 8.52X 10 of TBT as a transesterification catalyst were mixed together ^-4 g(2.50×10 ^-6 Moles) was charged to the reaction vessel as an EG solution. The reaction was carried out in a step 1 in which the heating tank was heated to 150 ℃ under a nitrogen atmosphere, stirred as necessary, and heated to 220 ℃ for 60 minutes under normal pressure to dissolve the starting materials, and in which the ester exchange reaction was carried out at 180 minutes under normal pressure to 250 ℃ to distill off a predetermined amount of methanol and held at 250 ℃ for 30 minutes. Thereafter, 3.20X 10 of TBT as a polymerization catalyst ^-3 g(9.40×10 ^-6 Moles) was dosed as EG solution.

As the 2 nd step, the temperature was raised from 250 ℃ to 270 ℃ over 90 minutes, the pressure was reduced from normal pressure to 0.2kPa over 90 minutes, and thereafter the reaction vessel was kept, and the produced water and excess EG were discharged to the outside. After the reaction was completed with a predetermined stirring torque, the resultant reaction product was taken out from the reaction vessel to obtain a polyester copolymer.

The reduced viscosity of the resulting polyester copolymer was 0.144 dl/g.

(example 7)

5.95g (0.0153 mol) of 2,12DNFE, 8.25g (0.0153 mol) of BNEF, 6.83g (0.0319 mol) of DPC, and 5.40X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-4 g(3.06×10 ^-6 Mol) was charged into a reaction vessel in the form of a 2% aqueous solution, and a polycarbonate copolymer was obtained in the same manner as in example 1.

The reduced viscosity of the resulting polycarbonate copolymer was 0.274 dl/g.

(example 8)

2.46g (0.0063 mol) of 2,12DNFE, 8.32g (0.0190 mol) of BPEF, 3.41g (0.0063 mol) of BNEF, 7.04g (0.0329 mol) of DPC, and 2.78X 10 calcium acetate monohydrate as a catalyst were mixed together ^-4 g(1.58×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and a polycarbonate copolymer was obtained in the same manner as in example 1.

The reduced viscosity of the resulting polycarbonate copolymer was 0.530 dl/g.

(example 9)

1.20g (0.0031 mol) of 2,12DNFE, 4.64g (0.0124 mol) of BNEO, 8.35g (0.0155 mol) of BNEF, 6.91g (0.0322 mol) of DPC, and 2.73X 10 of calcium acetate monohydrate as a catalyst ^-4 g(1.55×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and a polycarbonate copolymer was obtained in the same manner as in example 1.

The reduced viscosity of the polycarbonate copolymer obtained was 0.273 dl/g.

(example 10)

2,1 is1.24g (0.0032 mol) of 2DNFE, 11.21g (0.0256 mol) of BPEF, 1.72g (0.0032 mol) of BNEF, 7.12g (0.0332 mol) of DPC, and 2.81X 10 of calcium acetate monohydrate as a catalyst ^-4 g(1.60×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and a polycarbonate copolymer was obtained in the same manner as in example 1.

The reduced viscosity of the resulting polycarbonate copolymer was 0.394 dl/g.

(example 11)

1.00g (0.0033 mol) of 2,12DNF, 13.14g (0.0300 mol) of BPEF, 7.49g (0.0349 mol) of DPC, and 5.87X 10 of cesium carbonate as a catalyst were mixed ^-3 g(1.80×10 ^-5 Mole) was put into a reaction vessel as a 0.2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and the temperature was raised to 240 ℃ over 60 minutes under normal pressure with stirring as necessary to dissolve the raw materials.

In the step 1 of the reaction, the pressure was reduced from normal pressure to 13.3kPa for 40 minutes while maintaining 240 ℃ and then maintained at 13.3kPa for 60 minutes, and the produced phenol was discharged to the outside of the reaction vessel.

In the 2 nd step, the temperature of the heating tank was increased to 270 ℃ over 20 minutes, and the pressure was controlled to 0.200kPa or less over 30 minutes, and the produced phenol was discharged out of the reaction vessel. After the reaction was completed with a predetermined stirring torque, the reaction product was taken out of the reaction vessel to obtain a polycarbonate copolymer.

The reduced viscosity of the resulting polycarbonate copolymer was 0.444 dl/g. When the refractive index was measured at 20 ℃, nC ═ 1.649, nD ═ 1.657, ne ═ 1.665, nF ═ 1.678, and abbe number were 23. The NMR spectrum of the polycarbonate copolymer is shown in fig. 6.

(example 12)

14.06g (0.0362 mol) of 2,12DNFE, 7.91g (0.0369 mol) of DPC, and 3.19X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-4 g(1.81×10 ^-6 Mol) was charged into a reaction vessel in the form of a 0.2% aqueous solution, and the reaction vessel was similarly charged to example 1 except thatTo polycarbonate copolymers.

(example 13)

4.24g (0.0109 mol) of 2,12DNFE, 3.16g (0.0059 mol) of BNEF, 10.76g (0.0168 mol) of PFM, and 3.30X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-3 g(1.87×10 ^-5 Mol) was charged into a reaction vessel in the form of a 2% aqueous solution, and a polyester copolymer was obtained in the same manner as in example 5 except that.

The reduced viscosity of the resulting polyester copolymer was 0.587 dl/g.

(example 14)

5.78g (0.0149 mol) of 2,12DNFE, 7.93g (0.0347 mol) of BPA, 11.16g (0.0521 mol) of DPC and 8.74X 10 mol of cesium carbonate as a catalyst were mixed together ^-4 g(2.68×10 ^-6 Mole) was put into a reaction vessel as a 0.2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and the temperature was raised to 240 ℃ over 60 minutes under normal pressure with stirring as necessary to dissolve the raw materials.

The reduced viscosity of the polycarbonate copolymer obtained was 0.220 dl/g. When the refractive index was measured at 20 ℃, nC ═ 1.634, nD ═ 1.642, ne ═ 1.650, nF ═ 1.667, and the abbe number was 20. The NMR spectrum of the polycarbonate copolymer is shown in fig. 7.

(example 15)

14.06g (0.0362 mol) of 3,11DNFE, 7.91g (0.0369 mol) of DPC, and 1.91X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-3 g(1.09×10 ^-5 Mole) ofA polycarbonate copolymer was obtained in the same manner as in example 1, except that the polycarbonate copolymer was charged into a reaction vessel in the form of a 2% aqueous solution.

(example 16)

6.63g (0.0171 mol) of 3,11DNFE, 7.48g (0.0171 mol) of BPEF, 7.46g (0.0348 mol) of DPC, and 1.80X 10 of calcium acetate monohydrate as a catalyst were mixed together ^-3 g(1.02×10 ^-5 Mol) was charged into a reaction vessel in the form of a 2% aqueous solution, and a polycarbonate copolymer was obtained in the same manner as in example 1.

The reduced viscosity of the resulting polycarbonate copolymer was 0.355 dl/g.

(example 17)

7.89g (0.0180 mol) of BPEF, 2.39g (0.0385 mol) of EG, 2.49g (0.0128 mol) of DMT, 5.71g (0.0128 mol) of 2,12DNFM, and 1.98X 10 calcium acetate as a transesterification catalyst ^-2 g(1.12×10 ^-4 Mole) was charged into the reaction vessel as a 2% aqueous solution. In the step 1 of the reaction, while heating the heating tank to 150 ℃ under a nitrogen atmosphere and stirring it as necessary to dissolve the raw materials, the temperature was raised to 250 ℃ for 180 minutes under normal pressure to carry out the transesterification reaction, a predetermined amount of methanol was distilled off, and the reaction mixture was held at 250 ℃ for 30 minutes. Thereafter, 6.57X 10 of germanium oxide was used as a polymerization catalyst ^-3 g(6.28×10 ^-5 Moles) are dosed in the form of an aqueous solution.

As the 2 nd step, the temperature was raised from 250 ℃ to 270 ℃ over 90 minutes, the pressure was reduced from normal pressure to 0.2kPa over 90 minutes, and the produced water and excess EG were discharged to the outside of the reaction vessel. After the reaction was completed with a predetermined stirring torque, the resultant reaction product was taken out from the reaction vessel to obtain a polyester copolymer.

The reduced viscosity of the resulting polyester copolymer was 0.429 dl/g.

(example 18)

8.07g (0.0150 mol) of BNEF, 3.16g (0.0509 mol) of EG, 2.91g (0.0150 mol) of DMT, 6.66g (0.0150 mol) of 2,12DNFM, and 1.98X 10 of calcium acetate as a transesterification catalyst ^-2 g(1.12×10 ^-4 Mole) was charged into the reaction vessel as a 2% aqueous solution. In the step 1 of the reaction, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and the raw materials were dissolved by stirring as necessary, and at the same time, the temperature was raised to 250 ℃ over 180 minutes under normal pressure to perform an ester exchange reaction, a predetermined amount of methanol was distilled off, and the reaction was maintained at 250 ℃ for 30 minutes. Thereafter, 6.57X 10 of germanium oxide was used as a polymerization catalyst ^-3 g(6.28×10 ^-5 Moles) are dosed in the form of an aqueous solution.

The reduced viscosity of the resulting polyester copolymer was 0.407 dl/g.

Comparative example 1

4.48g (0.0102 mol) of BPEF, 9.64g (0.00238 mol) of 2,12-DHEDNT, 7.44g (0.0347 mol) of DPC, and 6.00X 10 of calcium acetate monohydrate as a catalyst ^-4 g(3.40×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and the raw materials were dissolved by heating the vessel to 150 ℃ under a nitrogen atmosphere, stirring the vessel if necessary, and raising the temperature to 220 ℃ under normal pressure for 60 minutes, to obtain a polycarbonate copolymer in the same manner as in example 1.

The reduced viscosity of the resulting polycarbonate copolymer was 0.274 dl/g. When the refractive index was measured at 20 ℃, nC ═ 1.686, nD ═ 1.697, ne ═ 1.708, nF ═ 1.730, and abbe number were 16.

Comparative example 2

14.16 parts (0.0323 moles) of BPEF, 7.06g (0.0329 moles) of DPC and 1.71X 10 parts of calcium acetate monohydrate as a catalyst ^-3 g(9.69×10 ^-6 Mole) was put into a reaction vessel in the form of a 0.2% aqueous solution, the temperature of the heating tank was heated to 150 ℃ under a nitrogen atmosphere, and stirring was carried out as needed under normal pressureA polycarbonate copolymer was obtained in the same manner as in example 1, except that the temperature was increased to 220 ℃ over 60 minutes to dissolve the raw materials.

The reduced viscosity of the resulting polycarbonate copolymer was 0.330 dl/g. When the refractive index was measured at 20 ℃, nC ═ 1.634, nD ═ 1.642, ne ═ 1.649, nF ═ 1.762, and the abbe number was 23.

Comparative example 3

12.84g (0.0293 mol) of BPEF, 1.32g (0.0033 mol) of 2,12-DHEDNT, 7.11g (0.0332 mol) of DPC, and 5.73X 10 of calcium acetate monohydrate as a catalyst ^-4 g(1.76×10 ^-6 Moles) was charged into a reaction vessel as a 0.2% aqueous solution, and the raw materials were dissolved by heating the vessel to 150 ℃ under a nitrogen atmosphere, stirring the vessel if necessary, and raising the temperature to 220 ℃ under normal pressure for 60 minutes, to obtain a polycarbonate copolymer in the same manner as in example 1.

The reduced viscosity of the polycarbonate copolymer obtained was 1.152 dl/g. When the refractive index was measured at 20 ℃, nC ═ 1.638, nD ═ 1.647, ne ═ 1.654, nF ═ 1.668, and the abbe number was 22.

Comparative example 4

NOVAREX7020R standard, manufactured by mitsubishi chemical engineering plastics corporation, was used. When the refractive index was measured at 20 ℃, nD was 1.586, and abbe number was 30.

The measurement results of the copolymers of the respective examples are shown in tables 1 and 2. The presence or absence of a sulfur-containing structure in the thermoplastic resin is shown in the table.

(acid gas generation)

The polycarbonate of comparative example 1 was evaluated for the generation of acid gas.

About 10mg of the sample (polycarbonate copolymer of comparative example 1) was placed in a heating furnace (infrared furnace), and the temperature was raised from room temperature to 330 ℃ at a temperature raising rate of 50 ℃ per minute under a helium atmosphere containing 20% oxygen, and the temperature was maintained for 30 minutes. The gas generated at this time was subjected to GC/MS measurement (GC analysis conditions: after maintaining at 40 ℃ for 5 minutes, the temperature was raised to 280 ℃ at 10 ℃ per minute, and the temperature was maintained for 5 minutes; ionization method: Electron impact ionization (EI)), whereby the generation of a sulfur-containing acidic gas was confirmed.

In the GC/MS measurement, TPD-GC/MS systems (heating furnace: origin system of Mitsubishi chemical Co., Ltd., GC: 6890 manufactured by Agilent technologies Co., Ltd., MS: 5973N manufactured by Agilent technologies Co., Ltd., column: Ultra) were used

)。

The polycarbonate copolymer of comparative example 1 generates sulfur dioxide as an acid gas when heated at 330 ℃ which is a temperature around the usual molding temperature.

The polycarbonate copolymer of example 1 has a Tg which is preferable in terms of high fluidity (molding processability) and minimum heat resistance, and has a higher refractive index than that of comparative example 2. In addition, by using the same amount of the dinaphthofuran compound as the amount of the dinaphthothiophene compound of comparative example 3, the same refractive index improving effect as that of comparative example 3 was observed, although the monomer containing no sulfur in the structure was used. Further, since a sulfur-free monomer was used, unlike comparative example 1, sulfur dioxide as an acid gas was not generated when heating was performed at 330 ℃.

The same sulfur-containing structural monomer as in comparative example 1 was used for the polycarbonate copolymer of comparative example 3. Therefore, it is considered that sulfur dioxide as an acid gas is generated when heating is performed at 330 ℃ which is a temperature around a normal molding temperature, as in comparative example 1.

The polycarbonate copolymers of examples 1 to 18 have a Tg which is preferable in view of high fluidity and minimum heat resistance, and have a higher refractive index than that of comparative example 4. In addition, monomers which do not contain sulfur in their structure are used. Therefore, unlike comparative example 1, it is considered that sulfur dioxide as an acid gas is not generated when heating is performed at 330 ℃.

In comparative example 2, the refractive index was 1.638. In comparative example 2, examples 1,2, 4,5, 8,10, 11, 16 and 17 using BPEF had refractive indices in the range of 1.647 to 1.686. From this, it was also confirmed that the refractive index of the thermoplastic resin can be increased by using the compound of the present disclosure as a polymerization monomer of the thermoplastic resin.

Further, it is clear from examples 5 and 13 that by copolymerizing PFM, the photoelastic coefficient is decreased, and a resin having a good balance among the photoelastic coefficient, refractive index, and Tg can be obtained.

(UV absorption Spectroscopy)

10mg of 2,12DNF was dissolved in 500mL of chloroform, and the UV absorption spectrum was measured by UV3150 manufactured by Shimadzu corporation. Further, the UV absorption spectrum of 2, 12-dihydroxydinaphthothiophene (hereinafter also referred to as "2, 12-DODNT") was also measured in the same manner as described above. The results are shown in FIG. 1.

As is clear from fig. 1, the absorption coefficient on the long wavelength side of the dinaphthofuran skeleton is increased as compared with the dinaphthothiophene skeleton. In the dinaphthothiophene skeleton, the thiophene ring and the naphthalene ring are significantly deformed because the sulfur atom in the skeleton is large, but in the dinaphthofuran skeleton, the deformation of the furan ring and the naphthalene ring can be suppressed because the sulfur atom is replaced by an oxygen atom having a smaller atomic size. As a result, it is considered that the dinaphthofuran skeleton has a conjugated structure which is more extended than the dinaphthothiophene skeleton, and thereby the absorption coefficient on the long wavelength side is increased. It is also considered that the dinaphthofuran skeleton exhibits a high refractive index in the same manner as the dinaphthothiophene skeleton.

(extension chain structure)

For compounds containing [ -O-Q ¹ -O-C(＝O)-]The polycarbonate of the repeating unit represented by (1) has a structure in which the distance between the etheric oxygen atom at one end of the repeating unit and the etheric oxygen atom at one end of the repeating unit adjacent to the other end side (carbonyl side) of the repeating unit is longestLike isomers are defined as extended chain structures.

A polycarbonate having a dihydroxy compound of 2,12DNF, namely, a polycarbonate containing Q was obtained by performing a structure optimization using a molecular force field MMFF using software PC Spartan Pro 1.0.5 manufactured by Wavefunction Co ¹ An extended chain structure of a polycarbonate having a repeating unit of a residue obtained by removing 2 hydroxyl groups from 2,12 DNF. The obtained extended chain structure is shown in FIG. 2.

The extended chain structure was also determined in the same manner as described above for the polycarbonate using 3,11DNF as the dihydroxy compound and the polycarbonate using 6,8DNF as the dihydroxy compound. The respective extension chain structures are shown in fig. 3 and 4.

In the case of 3,11DNF or 6,8DNF as the dihydroxy compound, the ring is oriented in a direction horizontal to the extension direction in the extended chain structure. Therefore, it is presumed that the polycarbonate structure using 3,11DNF or 6,8DNF as the dihydroxy compound has a relatively large birefringence.

On the other hand, in the case of 2,12DNF as the dihydroxy compound, the ring is not horizontal but inclined with respect to the extension direction. Therefore, it is considered that the birefringence is relatively small in the polycarbonate structure using 2,12DNF as the dihydroxy compound. From this viewpoint, 2,12DNF is particularly preferable from the viewpoint of birefringence.

Industrial applicability

According to the present disclosure there may be provided: a compound which, when used as a monomer of a thermoplastic resin having either or both of a carbonate bond and a polyester bond, can give a thermoplastic resin having a high refractive index, good moldability, and no risk of mold corrosion; a thermoplastic resin having a high refractive index, excellent moldability and no risk of corrosion of a mold; and an optical member and an optical lens comprising the above thermoplastic resin.

Claims

1. A compound represented by the following formula (f),

[ solution 1]

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

2. The compound of claim 1, wherein B is ¹ And B ² Is a hydroxyl group, which is represented by the following formula (f1),

[ solution 2]

In the formula (f1), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The optional substituents of the carbon atoms at the bonding positions and substitution positions of (1) to (6) and (8) to (13) are the same as those of the formula (f).

3. The compound of claim 1, wherein B is ¹ And B ² Being an ester group, the compound is represented by the following formula (f2),

[ solution 3]

In the formula (f2), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The number of the bonding position and the optional substituent of the carbon atom of the substitution position numbers 1 to 6,8 to 13 is the same as that of the formula (f);

4. The compound of claim 1, wherein B is ¹ And B ² Is a hydroxy ester group, which is represented by the following formula (f3),

[ solution 4]

In the formula (f3), L ¹ And L ² 、m、n、(L ¹ O) _m And (L) ² O) _n The number of the bonding position and the optional substituent of the carbon atom of the substitution position numbers 1 to 6,8 to 13 is the same as that of the formula (f);

B ⁵ and B ⁶ Each independently represents an alkylene group having 1 to 10 carbon atoms, which may have a substituent, an arylene group having 4 to 10 carbon atoms, which may have a substituent, or an aralkylene group having 6 to 12 carbon atoms, which may have a substituent.

5. The compound of any one of claims 1 to 4, wherein L is ¹ And L ² Each independently represents an alkylene group having 1 to 10 carbon atoms with or without a substituent.

6. A compound according to any one of claims 1 to 5 wherein m and n represent integers from 1 to 4.

7. The compound according to any one of claims 1 to 6, wherein (L) is ¹ O) _m Bonded to the carbon atom of substitution position number 2, said (L) ² O) _n Bonded to the carbon atom at substitution position number 12.

8. The compound according to any one of claims 1 to 7, wherein the carbon atoms at the substitution positions are numbered 1 to 6 and 8 to 13 and are not bonded (L) ¹ O) _m Or (L) ² O) _n To which a hydrogen atom is bonded.

9. A thermoplastic resin, comprising: a structure in which 2 or more 2-valent structural units are linked via a 2-valent linking group,

at least a portion of the 2-valent linking groups are carbonate linkages or ester linkages,

[ solution 5]

m represents an integer of 0 to 4;

n represents an integer of 0 to 4;

carbon atoms numbered 1 to 6 and 8 to 13 in the substitution positionIs not bonded (L) ¹ O) _m Or (L) ² O) _n Each of which is independently bonded with a hydrogen atom or an optional substituent.

10. The thermoplastic resin according to claim 9, wherein,

at least a part of the 2 or more valent-2 structural units is a structural unit represented by the formula (1); and at least one or more selected from the group consisting of a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and a structural unit represented by the following formula (8),

[ solution 6]

L ³ and L ⁴ Each independently represents an alkylene group having 1 to 10 carbon atoms and optionally having a substituent, an arylene group having 4 to 10 carbon atoms and optionally having a substituent, or an arylene group having a substituentAn aralkyl group having 6 to 12 carbon atoms as a substituent;

o represents an integer of 0 to 4;

p represents an integer of 0 to 4,

[ solution 7]

q represents an integer of 0 to 4;

r represents an integer of 0 to 4,

[ solution 8]

s represents an integer of 0 to 4;

t represents an integer of 0 to 4,

[ solution 9]

R ²² 、R ²³ and R ²⁴ Each independently represents a direct bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, an arylene group having 4 to 10 carbon atoms which may have a substituent, an aralkylene group having 6 to 12 carbon atoms which may have a substituent, or a group in which 2 or more groups selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which may have a substituent and an arylene group having 4 to 10 carbon atoms which may have a substituent are linked by an oxygen atom, a nitrogen atom having a substituent or not, or a carbonyl group;

R ²⁵ ～R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, an aryl group having 3 to 14 carbon atoms and optionally having a substituent, or an aryl group having 1 carbon atom and optionally having a substituent10 acyl group, C1-10 alkoxy group with or without substituent, C3-14 aryloxy group with or without substituent, C1-10 acyloxy group with or without substituent, amino group with or without substituent, C2-10 alkenyl group with or without substituent, C2-10 alkynyl group with or without substituent, silicon atom with substituent, halogen atom, nitro group or cyano group;

v represents an integer of 0 to 5,

[ solution 10]

u represents an integer of 0 to 4;

when u is 2 or more, each K ¹ The same or different;

[ solution 11]

In the formula (7), K ² Each independently represents a hydrogen atom, a carbon atom with or without a substituentA sub-number of 1 to 10 alkyl groups, substituted or unsubstituted aryl groups having 3 to 14 carbon atoms, substituted or unsubstituted acyl groups having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy groups having 3 to 14 carbon atoms, substituted or unsubstituted acyloxy groups having 1 to 10 carbon atoms, substituted or unsubstituted amino groups, substituted or unsubstituted alkenyl groups having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 10 carbon atoms, substituted silicon atoms, halogen atoms, nitro groups or cyano groups;

w represents an integer of 0 to 4;

when w is 2 or more, each K ¹ The same or different, and the same or different,

[ solution 12]

In the formula (8), one of the 2 connecting bonds is bonded to any one of the carbon atoms of the substituted position numbers 1-6, and the other connecting bond is bonded to any one of the carbon atoms of the substituted position numbers 8-13;

a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without a substituent, an aryl group having 3 to 14 carbon atoms with or without a substituent, an acyl group having 1 to 10 carbon atoms with or without a substituent, an alkoxy group having 1 to 10 carbon atoms with or without a substituent, an aryloxy group having 3 to 14 carbon atoms with or without a substituent, an acyloxy group having 1 to 10 carbon atoms with or without a substituent, an amino group having or without a substituent, an alkenyl group having 2 to 10 carbon atoms with or without a substituent, an alkynyl group having 2 to 10 carbon atoms with or without a substituent, a silicon atom with a substituent, a halogen atom, a nitro group or a cyano group are independently bonded to the carbon atoms not bonded to the connecting bond among the carbon atoms numbered 1 to 6 and 8 to 13 in the substitution position.

11. The thermoplastic resin of claim 9 or 10, wherein either or both of the carbonate linkage and the ester linkage comprises a carbonyl carbon from a carbonic acid diester represented by the following formula (o),

[ solution 13]

In the formula (, E) ⁵ And E ⁶ Each independently is an aliphatic hydrocarbon group having 1 to 18 carbon atoms and having or not having a substituent, or an aromatic hydrocarbon group having or not having a substituent;

E ⁵ and E ⁶ The same or different.

12. The thermoplastic resin of any of claims 9-11, wherein the reduced viscosity of the thermoplastic resin is from 0.15dL/g to 1.50 dL/g.

13. The thermoplastic resin according to any one of claims 9 to 12, wherein the glass transition temperature of the thermoplastic resin is from 100 ℃ to 180 ℃.

14. The thermoplastic resin according to any one of claims 9 to 13, wherein a refractive index of the thermoplastic resin is 1.62 or more.

15. An optical member comprising the thermoplastic resin as claimed in any one of claims 9 to 14.

16. An optical lens comprising the thermoplastic resin according to any one of claims 9 to 14.