JP7183299B2 - Thermoplastic resin for lens and lens containing same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin for lenses and a lens containing the same.

There is a strong demand for lower birefringence and improved aberration correction capability for plastic imaging lenses used in devices such as smartphones. Conventionally, in such an imaging lens, aberration correction is performed by combining a plurality of lenses having mutually different optical properties (refractive index, Abbe number) and by combining lens shapes.

For example, as a resin with a high refractive index and a low Abbe's number for use in imaging lenses, Patent Document 1 discloses a polycarbonate using a specific monomer without using bisphenol A as a raw material.

Incidentally, a polycarbonate using 2,2,4,4-tetramethyl-1,3-cyclobutanediol (hereinafter referred to as TMCBD) as a monomer is conventionally known (Patent Documents 2 to 6 and Non-Patent Document 1 ). Also, a method for producing TMCBD is described in Patent Document 7, and a method for producing a raw material for TMCBD is described in Non-Patent Document 2.

WO2017/010318 Japanese Patent Publication No. 38-26798 JP-A-63-92644 JP-A-2-222416 JP-A-11-240945 JP 2015-137355 A Japanese Patent Publication No. 8-506341

CAREY CECIL GEIGER, JACK D.DAVIES, WILLIAM H.DALY, Aliphatic-Aromatic Copolycarbonates Derived from 2,2,4,4-Tetramethyl-1,3-cyclobutanediol, Journal of Polymer Science: Part A: Polymer Chemistry, 1995, Vol. .33, 2317-2327 Bulletin of the Faculty of Engineering, Hokkaido University, 67:155-163(1973)

The imaging lens is designed by combining lenses having different optical characteristics as described above. Therefore, what kind of refractive index and Abbe number one lens should have depends on the refractive index and Abbe number of other lenses, and cannot be defined unconditionally.

On the other hand, there is a negative correlation between the refractive index and the Abbe number, in which a resin with a high refractive index has a low Abbe number and a resin with a low refractive index has a high Abbe number.

Therefore, even if a designer of an imaging lens tries to adopt a lens having a specific refractive index and a specific Abbe number, such a lens may not exist. There is a limit.

Also, even if there is a resin that can provide a specific refractive index and a specific Abbe number, other properties such as hue, heat resistance, moldability, and water absorption are not suitable as resins for imaging lenses. In this regard, there are also restrictions on lenses that can be adopted by imaging lens designers.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a thermoplastic resin for lenses that can provide a wide range of lens types so that imaging lens designers can adopt various types of lenses. .

（式中、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４は、夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基又は炭素原子数７～２０のアラルキルオキシ基、又はハロゲン原子を示し；シクロブタン環はシス・トランス異性体混合物、シス異性体単独、トランス異性体単独のいずれかを示す）；
ジヒドロキシ化合物又はジカルボン酸化合物に由来する第２の構造単位と
を有し、かつ
以下の数式（Ａ）を満たす屈折率（ｎ_Ｄ）及びアッベ数（ν）を有する、
レンズ用熱可塑性樹脂：
ｎ_Ｄ＜１．１５６×１０^－４×ν^２－１．２８９×１０^－２×ν＋１．８５３ （Ａ）
《態様２》
下記式（２）で表される炭酸ジエステルに由来する末端芳香族基をさらに含む、態様１に記載の熱可塑性樹脂：

（式中、Ｒ_５及びＲ_６は、夫々独立に、置換又は無置換の芳香族基である）。
《態様３》
前記第２の構造単位が、脂肪族ジヒドロキシ化合物、脂環式ジヒドロキシ化合物、複素環式ジヒドロキシ化合物及び芳香族ジヒドロキシ化合物、並びに脂肪族ジカルボン酸化合物、脂環式ジカルボン酸化合物、複素環式ジカルボン酸化合物及び芳香族ジカルボン酸化合物からなる群より選ばれた少なくとも１種の化合物からもたらされる、態様１又は２に記載の熱可塑性樹脂。
《態様４》
前記第１の構造単位を、５０ｍｏｌ％超９５ｍｏｌ％以下で含む、態様１～３のいずれか一項に記載の熱可塑性樹脂。
《態様５》
屈折率（ｎ_Ｄ）が、１．４７０超１．６００以下である、態様１～４のいずれか一項に記載の熱可塑性樹脂。
《態様６》
アッベ数（ν）が、２５以上５０以下の範囲である、態様１～５のいずれか一項に記載の熱可塑性樹脂。
《態様７》
以下の数式（Ｃ）を満たす屈折率（ｎ_Ｄ）及びアッベ数（ν）を有する、態様１～６のいずれか一項に記載の熱可塑性樹脂：
ｎ_Ｄ≧１．１５６×１０^－４×ν^２－１．２８９×１０^－２×ν＋１．８００ （Ｃ）
《態様８》
ガラス転移温度が、１３０℃～１７０℃の範囲である、態様１～７のいずれか一項に記載の熱可塑性樹脂。
《態様９》
縦１００ｍｍ×横１００ｍｍ×厚さ３ｍｍの成形板についてＪＩＳ Ｋ７３７３に準拠して測定した初期色相（ＹＩ_０）が、４．０以下である、態様１～９のいずれか一項に記載の熱可塑性樹脂。
《態様１０》
複素環式アミンを実質的に含んでいない、態様１～９のいずれか一項に記載の熱可塑性樹脂。
《態様１１》
ポリカーボネート又はポリエステルカーボネートである、態様１～１０のいずれか一項に記載の熱可塑性樹脂。
《態様１２》
前記第１の構造単位をもたらすジヒドロキシ化合物と、前記第２の構造単位をもたらすジヒドロキシ化合物と、炭酸ジエステルとを、アルカリ金属触媒及び／又はアルカリ土類金属触媒の存在下でエステル交換反応させることを特徴とする、態様１～１１のいずれか一項に記載の熱可塑性樹脂の製造方法。
《態様１３》
前記第１の構造単位をもたらすジヒドロキシ化合物と、前記第２の構造単位をもたらすジカルボン酸化合物と、炭酸ジエステルとを、チタン化合物触媒の存在下又はアルミニウム触媒及びリン化合物触媒の存在下でエステル化及び／又はエステル交換反応させることを特徴とする、態様１～１１のいずれか一項に記載の熱可塑性樹脂の製造方法。
《態様１４》
前記第１の構造単位をもたらすジヒドロキシ化合物の第三級アミン含有量が、１０００重量ｐｐｍ以下である、態様１２又は１３に記載の熱可塑性樹脂の製造方法。
《態様１５》
前記第１の構造単位をもたらすジヒドロキシ化合物のホウ酸含有量が、１００重量ｐｐｍ以下である、態様１２～１４のいずれか一項に記載の熱可塑性樹脂の製造方法。
《態様１６》
態様１～１１のいずれか一項に記載の熱可塑性樹脂を含む、光学レンズ。The inventors have found that the above problems can be solved by the present invention having the following aspects.
<<Aspect 1>>
A first structural unit derived from a dihydroxy compound represented by the following formula (1):

(wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, or carbon atoms an aralkyloxy group of numbers 7 to 20, or a halogen atom; a cyclobutane ring indicates either a cis/trans isomer mixture, a cis isomer alone, or a trans isomer alone);
a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound, and having a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (A),
Thermoplastics for lenses:
n _D <1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (A)
<<Aspect 2>>
The thermoplastic resin according to aspect 1, further comprising a terminal aromatic group derived from a diester carbonate represented by the following formula (2):

(wherein R ₅ and R ₆ are each independently a substituted or unsubstituted aromatic group).
<<Aspect 3>>
The second structural unit comprises an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, a heterocyclic dihydroxy compound, an aromatic dihydroxy compound, an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and a heterocyclic dicarboxylic acid compound. and an aromatic dicarboxylic acid compound, the thermoplastic resin according to aspect 1 or 2.
<<Aspect 4>>
The thermoplastic resin according to any one of aspects 1 to 3, comprising more than 50 mol% and 95 mol% or less of the first structural unit.
<<Aspect 5>>
The thermoplastic resin according to any one of aspects 1 to 4, which has a refractive index (n _D ) of more than 1.470 and not more than 1.600.
<<Aspect 6>>
The thermoplastic resin according to any one of aspects 1 to 5, which has an Abbe number (ν) in the range of 25 or more and 50 or less.
<<Aspect 7>>
The thermoplastic resin according to any one of aspects 1 to 6, which has a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (C):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.800 (C)
<<Aspect 8>>
The thermoplastic resin according to any one of aspects 1 to 7, which has a glass transition temperature in the range of 130°C to 170°C.
<<Aspect 9>>
The thermoplastic according to any one of aspects 1 to 9, wherein the initial hue (YI ₀ ) measured according to JIS K7373 for a molded plate of 100 mm long × 100 mm wide × 3 mm thick is 4.0 or less. resin.
<<Aspect 10>>
The thermoplastic resin according to any one of aspects 1-9, which is substantially free of heterocyclic amines.
<<Aspect 11>>
The thermoplastic resin according to any one of aspects 1-10, which is a polycarbonate or polyester carbonate.
<<Aspect 12>>
transesterifying a dihydroxy compound that provides the first structural unit, a dihydroxy compound that provides the second structural unit, and a diester carbonate in the presence of an alkali metal catalyst and/or an alkaline earth metal catalyst; A method for producing a thermoplastic resin according to any one of aspects 1 to 11, characterized in that:
<<Aspect 13>>
a dihydroxy compound providing the first structural unit, a dicarboxylic acid compound providing the second structural unit, and a carbonic acid diester are esterified in the presence of a titanium compound catalyst or in the presence of an aluminum catalyst and a phosphorus compound catalyst; / Or the method for producing a thermoplastic resin according to any one of aspects 1 to 11, characterized by transesterification.
<<Aspect 14>>
14. The method for producing a thermoplastic resin according to aspect 12 or 13, wherein the dihydroxy compound that provides the first structural unit has a tertiary amine content of 1000 ppm by weight or less.
<<Aspect 15>>
15. The method for producing a thermoplastic resin according to any one of aspects 12 to 14, wherein the dihydroxy compound that provides the first structural unit has a boric acid content of 100 ppm by weight or less.
<<Aspect 16>>
An optical lens comprising the thermoplastic resin according to any one of aspects 1-11.

FIG. 1 shows the relationship between the refractive index and the Abbe number of the thermoplastic resin of the present invention and conventional resins.

The thermoplastic resin for lenses of the present invention is not particularly limited as long as it is a thermoplastic resin having a structural unit derived from formula (1) described later, but it is at least one selected from the group consisting of polycarbonate, polyester carbonate and polyester. is preferable from the viewpoint of the effect of the present invention, and it is particularly preferable to be composed of polycarbonate or polyester carbonate. The present invention also relates to the use or method of use of a thermoplastic resin as described below for a lens.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４は、夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基又は炭素原子数７～２０のアラルキルオキシ基、又はハロゲン原子を示し；シクロブタン環は、シス・トランス異性体混合物、シス異性体単独、トランス異性体単独のいずれかを示す）；
ジヒドロキシ化合物又はジカルボン酸化合物に由来する第２の構造単位と
を有し、かつ
以下の数式（Ａ）を満たす屈折率（ｎ_Ｄ）及びアッベ数（ν）を有する：
ｎ_Ｄ＜１．１５６×１０^－４×ν^２－１．２８９×１０^－２×ν＋１．８５３ （Ａ）The thermoplastic resin for lenses of the present invention comprises a first structural unit derived from a dihydroxy compound represented by the following formula (1):

(wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, or carbon atoms an aralkyloxy group of number 7 to 20, or a halogen atom; a cyclobutane ring indicates either a cis/trans isomer mixture, a cis isomer alone, or a trans isomer alone);
a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound, and having a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (A):
n _D <1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (A)

As shown in FIG. 1, in conventional resins, the refractive index (n _D ) and Abbe number (ν) have a relationship that satisfies the following formula (B):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (B)

In contrast, the present inventors have found that the relationship between the refractive index and the Abbe number becomes specific from the conventional relationship when the thermoplastic resin contains the repeating unit of formula (1). Specifically, it was found that when the thermoplastic resin contained the repeating unit of formula (1), the Abbe number tended to be smaller for a specific refractive index than in the past.

The presence of a resin having such a relationship between the refractive index and the Abbe number allows the imaging lens designer to adopt various types of lenses, which is very advantageous in lens design. . Further, it has been found that the thermoplastic resin containing the repeating unit of formula (1) is also advantageous in properties required for lenses such as hue, moldability, heat resistance, and water absorption.

Although polycarbonates and their refractive indices have been known as thermoplastic resins using TMCBD as a monomer, it has not been known that such polycarbonates have a uniquely low Abbe number. Therefore, it was not known that such polycarbonates would be useful in designing lenses.

The reason why the thermoplastic resin of the present invention exhibits such a refractive index and Abbe number is not bound by theory, but the thermoplastic resin containing the repeating unit of formula (1) has a cyclobutane skeleton in the main chain However, it is possible that the direction of the main chain of the polymer is twisted in a complicated manner.

As used herein, “refractive index (n _D )” is the refractive index at a wavelength of 589 nm measured at 25° C. and measured by the method described in Examples.

The thermoplastic resin of the present invention has a refractive index (n _D ) in the range of more than 1.470 and less than 1.600. The refractive index (n _D ) may be 1.475 or higher, 1.480 or higher, 1.485 or higher, 1.490 or higher, 1.495 or higher, or 1.500 or higher, 1.590 or lower, 1 .570 or less, 1.550 or less, 1.530 or less, 1.520 or less, 1.510 or less, or 1.500 or less. For example, the refractive index (n _D ) may be 1.475 or more and 1.550 or less, 1.480 or more and 1.540 or less, or 1.485 or more and 1.530 or less. It may be 1.490 or more and 1.520 or less.

As used herein, the "Abbe number (ν)" is calculated using the following formula from refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm measured at 25°C, and these are measured by the method described in Examples:
ν=(n _D −1)/(n _F −n _C )
(Here, n _D : refractive index at a wavelength of 589 nm, n _C : refractive index at a wavelength of 656 nm, and n _F : refractive index at a wavelength of 486 nm).

The Abbe number (ν) of the thermoplastic resin of the present invention is preferably in the range of 25 or more and 50 or less. The Abbe number (ν) may be 28 or more, 30 or more, or 35 or more, or may be 45 or less, 42 or less, 40 or less, or 38 or less. For example, the Abbe number (ν) may be 28 or more and 45 or less, or may be 30 or more and 42 or less.

The thermoplastic resin of the present invention may have a refractive index (n _D ) and Abbe number (ν) that satisfy the following formula (C):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.800 (C)

However, the thermoplastic resin of the present invention may have a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (D):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+α (D)
where α is 1.830, 1.820, 1.810 or 1.805.

In addition, the thermoplastic resin in the present invention may have a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (E):
n _D <1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+β (E)
where β is 1.852, 1.850, 1.845 or 1.840.

The glass transition temperature of the thermoplastic resin in the present invention may be 130° C. or higher, 135° C. or higher, 140° C. or higher, 170° C. or lower, 160° C. or lower, 155° C. or higher, when measured by the method described in the Examples. °C or lower, or 150 °C or lower. For example, the glass transition temperature of the thermoplastic resin of the present invention is 130° C. or higher and 160° C. or lower, or 140° C. or higher and 150° C. or lower.

The viscosity average molecular weight of the thermoplastic resin in the present invention may be 15000 or more, 18000 or more, or 20000 or more, and may be 30000 or less, 25000 or less, or 22000 or less when measured by the method described in the Examples. may For example, the thermoplastic resin of the present invention may have a viscosity average molecular weight of 15,000 to 30,000 or 18,000 to 22,000.

The absolute value of the orientation birefringence (Δn) of the thermoplastic resin in the present invention is 8.0×10 −3 or less, 6.5×10 ⁻³ or less, 5.5×10 ⁻³ or less, when measured by the method described in Examples. It is preferably 0×10 ⁻³ or less, or 3.0×10 ⁻³ or less. Within such a range, the optical distortion is small, and it is suitable as an optical lens material.

The thermoplastic resin in the present invention preferably has a light transmittance of 30% or more, more preferably 40% or more, and still more preferably 45% or more at a wavelength of 320 nm, as measured by the method described in the Examples. Particularly preferably, it is 50% or more. Within such a range, the light resistance tends to be good.

The thermoplastic resin of the present invention preferably has a light transmittance of 50% or more, more preferably 55% or more, still more preferably 60% or more at a wavelength of 350 nm, as measured by the method described in the Examples. Particularly preferably, it is 65% or more. Within such a range, the light resistance tends to be good.

The initial hue (YI ₀ ) of the thermoplastic resin of the present invention is 10.0 or less, 8.0 or less, 7.0 or less, or 6.0 or less when measured by the method described in the Examples. is preferred.

The hue (YI ₁ ) after the 1000-hour weather resistance test of the thermoplastic resin in the present invention is 13.0 or less, 12.0 or less, 10.0 or less, 9.0 or less, when measured by the method described in the Examples. It is preferably 0 or less, or 8.0 or less. Also, the color difference (ΔYI=YI ₁ -YI ₀ ) from the initial hue is preferably 7.0 or less, 6.0 or less, 5.0 or less, 3.0 or less, or 2.0 or less.

The thermoplastic resin in the present invention preferably contains more than 50 mol % and 95 mol % or less of the first structural unit from the viewpoint of obtaining physical properties suitable as a lens resin. The first structural unit may be 55 mol% or more, 60 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, or 85 mol% or more, and 90 mol% or less, 85 mol% or less, or 80 mol% or less. It may be contained in the thermoplastic resin. For example, the first structural unit may be 60 mol % or more and 90 mol % or less, or 70 mol % or more and 90 mol % or less. The composition ratio of structural units can be measured by the ¹ H NMR method.

The thermoplastic resin in the present invention preferably contains 5 mol % or more and less than 50 mol % of the second structural unit from the viewpoint of obtaining physical properties suitable as a lens resin. The second structural unit may be 10 mol% or more, 15 mol% or more, 20 mol% or more, or 25 mol% or more, and 45 mol% or less, 40 mol% or less, 30 mol% or less, 25 mol% or less, or 20 mol% or less. may be contained in the thermoplastic resin. For example, the second structural unit may be 10 mol % or more and 30 mol % or less. The composition ratio of structural units can be measured by the ¹ H NMR method.

Hereinafter, the thermoplastic resin of the present invention will be described by taking polycarbonate, polyester carbonate and polyester as examples.

In the present specification, the term "structural unit derived from a dihydroxy compound" refers to the structural unit of the portion of the dihydroxy compound excluding the dihydroxy group, as long as the thermoplastic resin can provide the advantageous effects of the present invention. Say. Therefore, for example, when the "dihydroxy compound" forms two ester bonds in the thermoplastic resin of the present invention, the "structural unit derived from the dihydroxy compound" refers to of the repeating units, excluding the two ester bonds. A "structural unit derived from a dicarboxylic acid compound" is also interpreted in the same manner.

Therefore, the first structural unit derived from the dihydroxy compound represented by formula (1) is the portion of the following structure excluding the linking group X in the thermoplastic resin:

The linking groups X can each have a different structure in the thermoplastic resin, for example each independently selected from the group consisting of an ester bond and a carbonate bond. The linking group X may be a linking group that links to another "first structural unit derived from a dihydroxy compound", and links "a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound". It may be a linking group, or a linking group for linking with another repeating unit.

Denoting the first structural unit as A ₁ and denoting the second structural unit as A ₂ , the thermoplastic resin of the present invention comprises -(X-A ₁ )-, -(X-A ₂ )-, and/ or -(XA ₁ -XA ₂ )-. The thermoplastic resin of the present invention may be a random polymer, an alternating polymer, or a block polymer.

<Polycarbonate>
The polycarbonate in the present invention is a thermoplastic resin having at least a carbonate group as a linking group. Obtained by reacting with the body. In particular, the polycarbonate obtained by the transesterification reaction with a carbonic acid diester in the present invention does not contain pyridine or its acid chloride as compared with the polycarbonate obtained by using phosgene or the like with pyridine as a catalyst, so that the hue is excellent. ing. Therefore, the polycarbonate in the present invention preferably does not substantially contain pyridine. For example, pyridine or its acid chloride is measured by ¹ H NMR, 1,1,2,2-tetrabromoethane is used as an internal standard, and the signal intensity ratio based on the internal standard and pyridine or its acid chloride is obtained, It can be 500 ppm by weight or less, 100 ppm by weight or less, or 50 ppm by weight or less.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４は、夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基、又はハロゲン原子を示し；シクロブタン環は、シス・トランス異性体混合物、シス異性体単独、トランス異性体単独のいずれかを示す）。<Dihydroxy compound that provides the first structural unit>
The polycarbonate in the present invention has a first structural unit derived from a dihydroxy compound represented by the following formula (1):

(wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryloxy group having 6 to 10 carbon atoms, carbon atom an aralkyloxy group of numbers 7 to 20, or a halogen atom; a cyclobutane ring indicates either a cis/trans isomer mixture, a cis isomer alone, or a trans isomer alone).

In formula (1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It represents an aralkyloxy group having 7 to 20 carbon atoms or a halogen atom. In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. is preferably an aryl group, more preferably a methyl group.

Examples of the dihydroxy compound represented by the formula (1) include 2-methyl-1,3-cyclobutanediol, 2,4-dimethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 2-ethyl-1,3-cyclobutanediol, 2,4-diethyl-1,3-cyclobutanediol, 2,2,4,4-tetraethyl-1,3-cyclobutanediol, 2-butyl -1,3-cyclobutanediol, 2,4-dibutyl-1,3-cyclobutanediol, 2,2,4,4-tetrabutyl-1,3-cyclobutanediol and the like. The most preferred dihydroxy compound is 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Two or more of these dihydroxy compounds may be used in combination.

The dihydroxy compound represented by formula (1) is preferably a cis-trans isomer mixture. Although the ratio is not limited, the lower limit of the cis isomer ratio is preferably 30 mol% or more, more preferably 45 mol% or more, and even more preferably 50 mol% or more. The upper limit of the cis isomer ratio is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less. When the cis isomer is in this range, the polymer tends to have good moldability. The cis isomer ratio can be measured by the ¹ H NMR method.

In order to produce the dihydroxy compound containing a cyclobutane ring represented by the formula (1), the ketene represented by the following formula (10) is added or dimerized to form a diketene, and then hydrogenated to form cyclobutane. Dihydroxy compounds containing rings can be synthesized.

（式（１０）中、Ｒ_１９、Ｒ_２０は夫々独立に、水素原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキルオキシ基、又はハロゲン原子を示す。）

(In formula (10), R ₁₉ and R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, , a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. represents an aralkyloxy group or a halogen atom.)

Synthesis examples of 2,2,4,4-tetramethyl-1,3-cyclobutanediol preferably used in the present invention include the following synthesis examples (I).

Synthesis Example (I) is a method of producing isobutyric acid as a starting material by adding dimethylketene produced by thermal decomposition or proceeding with a dimerization reaction, followed by hydrogenation. Here, using isobutyric anhydride or isobutyric acid as a raw material is an industrially advantageous method, which is described in detail in Patent Document 7.

In the synthesis example of (I) above, in the production of ketene by pyrolysis, various phosphorus compounds represented by triethyl phosphate are added as a catalyst, and a small amount of a tertiary amine compound is added to improve the yield. is described in a research report of Hokkaido University (Non-Patent Document 1).

The present inventors have found that when a dihydroxy compound that provides the first structural unit obtained by such a production method is used as a monomer for a thermoplastic resin, the tertiary amine remaining in the dihydroxy compound is It has been found to adversely affect hue and transparency. Even if a quaternary amine such as tetramethylammonium hydroxide is used as a polymerization catalyst, the color is not deteriorated, but a large amount of the tertiary amine remains in the dihydroxy compound that provides the first structural unit. It was unexpected that the hue of the polymer deteriorated in some cases.

Therefore, the amount of tertiary amine contained in the dihydroxy compound represented by the formula (1) is preferably 1000 ppm by weight or less, preferably 500 ppm by weight or less, and more preferably 100 ppm by weight or less. However, the dihydroxy compound may have a tertiary amine content of 0.1 ppm by weight or more, 1.0 ppm by weight or more, 10 ppm by weight or more, or 100 ppm by weight or more. Specific examples of tertiary amines include trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline and dimethylaniline. In particular, as a tertiary amine, triethylamine is preferably used from an industrial point of view. The tertiary amine content in the dihydroxy compound can be quantified by ion chromatography using a cation exchange column and an electrical conductivity detector. In addition, in the present invention, the dihydroxy compound represented by the formula (1) may be one obtained by using a tertiary amine in the production of the dihydroxy compound.

Other methods for producing dimethylketene include decarboxylation of dimethylmalonic anhydride, thermal decomposition of N-isobutyrylphthalimide, and α-carbomethoxy-α,β-dimethyl-β-butyrolactone. and a method by thermal decomposition of dimethylketene dimer.

As a method for adding hydrogen to the cyclic diketone after the addition of dimethylketene or the dimerization reaction, a method using a metal hydride and a method using hydrogen gas in the presence of a metal catalyst are generally used. Examples of the method using a metal hydride include a method using an aluminum-based reducing agent such as lithium aluminum hydride and a method using a boron-based reducing agent such as sodium borohydride. For industrial use, a boron-based reducing agent is suitable because of the stability of the compound and ease of handling, and sodium borohydride is often used as the reducing agent. It is characterized by the production of boric acid as a by-product in the hydrogenation reaction using a boron-based reducing agent.

The present inventors have found that when a dihydroxy compound that provides the first structural unit obtained by such a production method is used as a monomer for a thermoplastic resin, the boric acid remaining in the dihydroxy compound is responsible for the hue and color of the thermoplastic resin. It has been found to adversely affect transparency.

Therefore, the boric acid content contained in the dihydroxy compound represented by the formula (1) is 100 ppm by weight or less, preferably 80 ppm by weight or less, more preferably 50 ppm by weight or less, and further preferably 20 ppm by weight or less. preferable. However, the boric acid content of the dihydroxy compound may be 0.1 weight ppm or more, 1.0 weight ppm or more, 5 weight ppm or more, or 10 weight ppm or more. Boric acid content in dihydroxy compounds can be quantified using gas chromatography-mass spectrometry by derivatization with a silylating agent. In addition, in the present invention, the dihydroxy compound represented by the formula (1) can be one obtained by using a boron-based reducing agent when producing the dihydroxy compound.

<Dihydroxy compound leading to second structural unit>
The polycarbonate in the present invention contains a first structural unit derived from the dihydroxy compound represented by formula (1) and a second structural unit derived from the dihydroxy compound. The dihydroxy compound that provides the second structural unit is not particularly limited as long as it is a compound that can serve as a structural unit of polycarbonate for lenses.

For example, as the dihydroxy compound that provides the second structural unit, a linear or cyclic, substituted or unsubstituted hydrocarbon-based dihydroxy compound that may have a heteroatom and/or may be branched , in particular, hydrocarbon-based dihydroxy compounds having 2 to 50 carbon atoms.

Specifically, dihydroxy compounds that provide the second structural unit may include aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, heterocyclic dihydroxy compounds, and aromatic dihydroxy compounds, particularly WO2004 /111106 pamphlet, WO 2011/021720 pamphlet, and dihydroxy compounds having oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol. Two or more of these dihydroxy compounds may be used in combination.

（式（３）中、ｍは２～１２の整数を示す）Examples of the aliphatic dihydroxy compound include linear or branched aliphatic dihydroxy compounds having 2 to 30 carbon atoms which may have a substituent. For example, as the aliphatic dihydroxy compound, a dihydroxy compound represented by the following formula (3) can be preferably used.

(In formula (3), m represents an integer of 2 to 12)

Specific examples of aliphatic dihydroxy compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2- ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2 -ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol etc.

Examples of the alicyclic dihydroxy compound include monocyclic or polycyclic alicyclic dihydroxy compounds having 3 to 30 carbon atoms, which may have a substituent. Specific examples of alicyclic dihydroxy compounds include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, and pentacyclopentadecanedimethanol. Preferred are cyclohexanedimethanol, tricyclodecanedimethanol and pentacyclopentadecanedimethanol.

Examples of the heterocyclic dihydroxy compound include optionally substituted monocyclic, polycyclic or condensed polycyclic heterocyclic dihydroxy compounds having 3 to 30 carbon atoms. Specific examples of heterocyclic dihydroxy compounds include 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, isosorbide and isomannide. , and isoidide. Isosorbide is preferred.

Examples of aromatic dihydroxy compounds include monocyclic, polycyclic or condensed polycyclic aromatic dihydroxy compounds having 6 to 50 carbon atoms, which may have a substituent.

As the aromatic dihydroxy compound, a dihydroxy compound represented by the following formula (4) can be used.

（式（４）中、Ｗは下記式（５）～（８）からなる群より選択される少なくとも１種の二価の有機残基、単結合、又は下記式（９）のいずれかの結合を表し、Ｘ及びＹはそれぞれ独立して０又は１～４の整数であり、Ｒ_７及びＲ_８はそれぞれ独立して、ハロゲン原子、又は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数６～１０のアリール基、炭素原子数７～２０のアラルキル基、炭素原子数６～１０のアリールオキシ基、及び炭素原子数７～２０のアラルキルオキシ基からなる群より選択される有機残基を表す。Ｌ_１およびＬ_２は、それぞれ独立に２価の連結基（例えば、メチレン基）を示し、oおよびpはそれぞれ独立に０または１を示す）

(In the formula (4), W is at least one divalent organic residue selected from the group consisting of the following formulas (5) to (8), a single bond, or any bond of the following formula (9) , X and Y are each independently an integer of 0 or 1 to 4, R ₇ and R ₈ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom -10 alkoxy groups, 6 to 20 carbon atom cycloalkyl groups, 6 to 20 carbon atom cycloalkoxy groups, 6 to 10 carbon atom aryl groups, 7 to 20 carbon atom aralkyl groups, carbon atoms represents an organic residue selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms, L ₁ and L ₂ each independently represent a divalent linking group (eg , methylene group), and o and p each independently represent 0 or 1)

（式（５）中、Ｒ_９、Ｒ_１０、Ｒ_１１及びＲ_１２はそれぞれ独立して、水素原子、ハロゲン原子又は炭素数１～３のアルキル基を表す。）

(In formula (5), R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（６）中、Ｒ_１３及びＲ_１４はそれぞれ独立して、水素原子、ハロゲン原子又は炭素数１～３のアルキル基を表す。）

(In formula (6), R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（７）中、Ｕは４～１１の整数を表し、かかる複数のＲ_１５及びＲ_１６はそれぞれ独立して水素原子、ハロゲン原子、及び炭素数１～３のアルキル基から選択される基を表す。）

(In formula (7), U represents an integer of 4 to 11, and each of the plurality of R ₁₅ and R ₁₆ is a group independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. represents.)

（式（８）中、Ｒ_１７及びＲ_１８はそれぞれ独立して、水素原子、ハロゲン原子、及びハロゲン原子で置換されていてもよい炭素数１～１０の炭化水素基から選択される基を表す。）

(In formula (8), R ₁₇ and R ₁₈ each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom. .)

前記式（４）におけるＷが単結合である構成単位を誘導するジヒドロキシ化合物の具体例としては、４，４’－ビフェノール及び４，４’－ビス（２，６－ジメチル）ジフェノール等が挙げられる。

Specific examples of the dihydroxy compound that induces a structural unit in which W is a single bond in the formula (4) include 4,4'-biphenol and 4,4'-bis(2,6-dimethyl)diphenol. be done.

Specific examples of dihydroxy compounds from which W is a structural unit of formula (5) include α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl )-m-diisopropylbenzene (usually referred to as "bisphenol M"), α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene and the like. Bisphenol M is preferred.

Specific examples of dihydroxy compounds from which W is a structural unit of formula (6) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. , and 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(hydroxyethoxy)phenyl)fluorene (commonly referred to as “BPEF”), 9,9-bis (4-(hydroxyethoxy)-3-phenylphenyl)fluorene and the like. 9,9-bis(4-hydroxy-3-methylphenyl)fluorene is preferred.

Specific examples of dihydroxy compounds from which W is a structural unit of formula (7) include 1,1-bis(4-hydroxyphenyl)cyclohexane (usually referred to as “bisphenol Z”), 1,1-bis (4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, and 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-3methylcyclohexane (commonly referred to as "bisphenol 3MZ"), 1, 1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the like. Preferably 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3methylphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5- It is trimethylcyclohexane.

Specific examples of dihydroxy compounds from which W is a structural unit of formula (8) include 4,4′-dihydroxydiphenylmethane, 2,4′-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, bis(4- hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1 - bis(4-hydroxy-2-phenyl)-1-phenylethane, 1,1-bis(4-hydroxy-2-chlorophenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as "bisphenol A ”), 2,2-bis(4-hydroxy-3-methylphenyl)propane (commonly referred to as “bisphenol C”), 2,2-bis(3-phenyl-4-hydroxyphenyl) Propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4- hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy phenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 4 ,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4- hydroxyphenyl)decane, 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, and the like. Bisphenol A, bisphenol C, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 1,1-bis(4-hydroxyphenyl)decane are preferred.

Specific examples of dihydroxy compounds from which W is any of the structural units represented by formula (9) include 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, -ter, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4' -dihydroxydiphenyl sulfide and bis(3,5-dimethyl-4-hydroxyphenyl) sulfone. Preferred are 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxydiphenyl sulfide.

Among the above dihydric phenols, bisphenol M in formula (5), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene in formula (6), and 1,1-bis(4- hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bisphenol A in formula (8), bisphenol C, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)decane, and in formula (9) 3,3′-dimethyl-4,4′-dihydroxy Diphenyl sulfide and 4,4'-dihydroxydiphenyl sulfide are preferred. Preferably 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) ) is hexafluoropropane.

Furthermore, the dihydric phenol derived from structural units other than formula (4) is preferably 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms, 3-(4 -hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol, 6,6′-dihydroxy-3,3 ,3′,3′-tetramethylspirobiindane, 1-methyl-1,3-bis(4-hydroxyphenyl)-3-isopropylcyclohexane, 1-methyl-2-(4-hydroxyphenyl)-3-[ Examples include 1-(4-hydroxyphenyl)isopropyl]cyclohexane, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, and ethylene glycol bis(4-hydroxyphenyl) ether. Preferred is 6,6'-dihydroxy-3,3,3',3'-tetramethylspirobiindane.

Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and the like. These compounds may be used individually by 1 type, and may use 2 or more types together.

Dihydroxy compounds that provide the second structural unit include cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, isosorbide, bisphenol M, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1 , 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bisphenol A, bisphenol C, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)decane, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 4 ,4′-dihydroxydiphenyl sulfide, 6,6′-dihydroxy-3,3,3′,3′-tetramethylspirobiindane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 6,6′-dihydroxy-3,3,3′, 3'-Tetramethylspirobiindane is more preferred.

For other details of the dihydroxy compound that provides such a second structural unit, refer to documents disclosing dihydroxy compounds related to polycarbonates, such as WO03/080728, JP-A-6-172508, JP-A-8-27370, Japanese Unexamined Patent Application Publication Nos. 2001-55435 and 2002-117580 can be referred to. The illustrated compounds are examples of dihydroxy compounds that can be used as structural units of the thermoplastic resin in the present invention, and are not limited to these.

<Carbonic acid diester>
The polycarbonate in the present invention can be obtained by transesterifying the dihydroxy compound that provides the first structural unit and the dihydroxy compound that provides the second structural unit with diester carbonate. The type of diester carbonate is not particularly limited as long as the polycarbonate in the present invention can be produced.

（式（２）中、Ｒ_５、Ｒ_６は夫々独立に、置換若しくは無置換の芳香族基である。）Preferably, the carbonic acid diester is a compound having the following formula (2):

(In Formula (2), R ₅ and R ₆ are each independently a substituted or unsubstituted aromatic group.)

The polycarbonate of the present invention has a terminal aromatic group, particularly a terminal phenyl group, derived from the diester carbonate represented by the above formula (2), and when measured by the method described in Examples, the terminal aromatic group The concentration is 30 μeq/g or more, preferably 40 μeq/g or more, particularly preferably 50 μeq/g or more, and the upper limit is preferably 160 μeq/g or less, more preferably 140 μeq/g or less, further preferably 100 μeq/g or less. is.

If the concentration of the terminal aromatic group is within such a range, the hue immediately after polymerization and during molding tends to be good, the hue after exposure to ultraviolet rays is good, and the heat stability tends to be good. In order to control the concentration of the terminal aromatic group, in addition to controlling the molar ratio of the raw material dihydroxy compound and carbonic acid diester, methods such as controlling the type and amount of the catalyst during the transesterification reaction, and controlling the pressure and temperature during polymerization, etc. is mentioned.

<<Manufacturing method of polycarbonate>>
According to the method for producing a polycarbonate of the present invention, a dihydroxy compound that provides a first structural unit, a dihydroxy compound that provides a second structural unit, and a diester carbonate are reacted in the presence of an alkali metal catalyst and/or an alkaline earth metal catalyst. including transesterifying with By the method of the present invention, the above-described polycarbonate of the present invention can be obtained. Therefore, for each configuration of the production method of the present invention, reference can be made to each configuration described for the polycarbonate of the present invention.

The polycarbonate in the present invention can be produced by a reaction means known per se for producing ordinary polycarbonates, for example, a method of reacting a dihydroxy component with a carbonate precursor such as a diester carbonate. Next, the basic means of these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of the aromatic dihydroxy component is stirred with the carbonic acid diester under an inert gas atmosphere while heating to distill off the resulting alcohol or phenol. . Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenols produced are distilled off. Moreover, you may add a terminal terminator, an antioxidant, etc. as needed.

Carbonic acid diesters used in the transesterification reaction include esters such as optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate and m-cresyl carbonate. Among them, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate to be used is preferably 0.97-1.10 mol, more preferably 1.00-1.06 mol, per 1 mol of the total dihydroxy compound.

In the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, etc. of alkali metals and alkaline earth metals are preferably used. They can be used singly or in combination.

Alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium Stearate, Potassium Stearate, Cesium Stearate, Lithium Stearate, Sodium Borohydride, Sodium Benzoate, Potassium Benzoate, Cesium Benzoate, Lithium Benzoate, Disodium Hydrogen Phosphate, Dipotassium Hydrogen Phosphate, Phosphorus Dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol and the like are exemplified.

Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetic acid. Barium and the like are exemplified.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having an alkyl or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. mentioned. Examples include bases or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like.

Other transesterification catalysts include salts of zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, Tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead acetate ( IV) Titanium tetrabutoxide (IV) and the like are used. Catalysts used in WO 2011/010741 and JP 2017-179323 A may be used.

Furthermore, a catalyst comprising aluminum or a compound thereof and a phosphorus compound may be used. In that case, it may be 8 × 10 ^-5 mol or more, 9 × 10 ^-5 mol or more, 1 × 10 ^-4 mol or more, or 1 × 10 ^-3 mol or less, 8×10 ⁻⁴ mol or less, or 6×10 ⁻⁴ mol or less.

Examples of aluminum salts include organic acid salts and inorganic acid salts of aluminum. Examples of organic acid salts of aluminum include carboxylates of aluminum, and specific examples include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, Mention may be made of aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate and aluminum salicylate. Examples of inorganic acid salts of aluminum include aluminum chloride, aluminum hydroxide, aluminum hydroxychloride, aluminum carbonate, aluminum phosphate, and aluminum phosphonate. Aluminum chelate compounds can include, for example, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum ethylacetoacetate diiso-propoxide.

Phosphorus compounds include, for example, phosphonic acid-based compounds, phosphinic acid-based compounds, phosphine oxide-based compounds, phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds. Among these, phosphonic acid-based compounds, phosphinic acid-based compounds, and phosphine oxide-based compounds can be mentioned in particular, and phosphonic acid-based compounds can be particularly mentioned.

The amount of these polymerization catalysts to be used is preferably 0.1 μmol to 500 μmol, more preferably 0.5 μmol to 300 μmol, still more preferably 1 μmol to 100 μmol, per 1 mol of the dihydroxy component.

Also, a catalyst deactivator can be added in the latter stage of the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acid are preferable. Further preferred are salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate and salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate.

Examples of sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, Octyl p-toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and/or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 mol per 1 mol of the catalyst. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.

<Polyester carbonate>
The polyester carbonate in the present invention is a thermoplastic resin having at least a carbonate group and an ester group as linking groups, and is produced, for example, from a dihydroxy compound represented by the above formula (1) and a dicarboxylic acid compound. In this specification, a dicarboxylic acid compound means a compound having at least two carboxylic acid groups or carboxylic acid ester groups. Moreover, the polyester carbonate in the present invention may further have a third structural unit derived from a dihydroxy compound different from the dihydroxy compound represented by the above formula (1).

Regarding the dihydroxy compound that provides the first structural unit, the dihydroxy compound that provides the third structural unit, and the polycarbonate portion of the polyester carbonate in the present invention, the dihydroxy compound that provides the first structural unit, the dihydroxy compound that provides the first structural unit, and the second Reference can be made to the description of dihydroxy compounds and polycarbonate moieties leading to 2 structural units.

As the dicarboxylic acid compound that provides the second structural unit of the polyester carbonate in the present invention, two hydroxy groups of the dihydroxy compound that provides the second structural unit described in the polycarbonate described above are combined with a carboxylic acid group and/or a carboxylic acid group. A compound substituted with an ester group can be used.

For example, the dicarboxylic acid compound that provides the second structural unit of the polyester carbonate in the present invention includes malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, and the like. Alicyclic dicarboxylic acid compounds such as 2,6-decalinedicarboxylic acid, monocyclic aromatic dicarboxylic acid compounds such as heterocyclic dicarboxylic acid compounds and phthalic acid, anthracenedicarboxylic acid, phenanthenedicarboxylic acid Polycyclic aromatic dicarboxylic acid compounds such as can be mentioned, mainly 1,4-cyclohexanedicarboxylic acid, adamantanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-bis ( Carboxymethoxy)-1,1'binaphthyl, 9,9'-bis(2-carboxyethoxy)fluorene or ester-forming derivatives thereof (eg, dimethyl terephthalate) are preferred. These may be used alone or in combination of two or more.

Examples of carbonate precursors used in the production of polyester carbonate in the present invention include phosgene, diphenyl carbonate, bischloroformates of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl. Carbonate, dinaphthyl carbonate and the like can be mentioned, and among them diphenyl carbonate is preferable.

<<Method for producing polyester carbonate>>
As a method for producing polyester carbonate in the present invention, a method used for producing ordinary polyester carbonate is arbitrarily adopted. For example, a reaction of a dihydroxy compound with a dicarboxylic acid or a dicarboxylic acid chloride with phosgene, or a transesterification reaction with a dihydroxy compound, a dicarboxylic acid and a bisaryl carbonate are preferably employed.

The reaction of the dihydroxy compound, dicarboxylic acid or its acid chloride with phosgene is carried out in a non-aqueous system in the presence of an acid binder and a solvent. Examples of acid-binding agents include pyridine, dimethylaminopyridine and tertiary amines. Halogenated hydrocarbons such as methylene chloride and chlorobenzene are used as the solvent. As a molecular weight modifier, it is desirable to use a terminal terminator such as phenol or p-tert-butylphenol. The reaction temperature is usually 0 to 40° C., and the reaction time is preferably several minutes to 5 hours.

In the transesterification reaction, a dihydroxy compound, a dicarboxylic acid or a diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and the mixture is reacted under reduced pressure at usually 120 to 350°C, preferably 150 to 300°C. The degree of pressure reduction is changed stepwise, and finally the pressure is reduced to 133 Pa or less to distill out the produced alcohols out of the system. The reaction time is usually about 1 to 4 hours. Moreover, a polymerization catalyst can be used in order to promote the reaction in the transesterification reaction. As such a polymerization catalyst, it is preferable to use an alkali metal compound, an alkaline earth metal compound or a heavy metal compound as a main component and, if necessary, a nitrogen-containing basic compound as an auxiliary component.

Alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate. , potassium stearate, lithium stearate, sodium salt, potassium salt, lithium salt of bisphenol A, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, and strontium carbonate. , calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

Nitrogen-containing basic compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.

As other transesterification catalysts, the catalysts exemplified as transesterification catalysts in the above-described method for producing polycarbonate can be used in the same manner.

After the polymerization reaction of the polyester carbonate of the present invention is completed, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability. In general, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Esters, phosphoric acid, phosphoric acid, phosphoric acid such as phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphites such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorus phosphates such as dioctyl acid and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; ) Phosphines such as ethane, boric acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halogens such as stearic chloride, benzoyl chloride, and p-toluenesulfonic acid chloride Alkyl sulfates such as dimethyl sulfate, organic halides such as benzyl chloride, and the like are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol, relative to the catalyst amount. If it is less than 0.01 times the molar amount of the catalyst, the deactivation effect becomes insufficient, which is not preferable. On the other hand, when the amount is more than 50 times the molar amount of the catalyst, the heat resistance is lowered and the molded article tends to be colored, which is not preferable.

After deactivating the catalyst, a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 13.3 to 133 Pa and a temperature of 200 to 320° C. may be provided.

"polyester"
The polyester in the present invention is a thermoplastic resin having at least an ester group as a linking group, and is produced, for example, from a dihydroxy compound represented by the above formula (1) and a dicarboxylic acid compound.

Regarding the dihydroxy compound that provides these first structural units in the polyester of the present invention, the same can be said for the polycarbonate described above. As for the dicarboxylic acid compound that provides the second structural unit, the same can be said for the polyester carbonate described above.

<<Manufacturing method of polyester>>
When the thermoplastic resin of the present invention is a polyester, a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof are subjected to an esterification reaction or a transesterification reaction, and the resulting reaction product is subjected to a polycondensation reaction to obtain the desired A high molecular weight substance may be used.

As the polymerization method, it can be produced by selecting an appropriate method from known methods such as a direct polymerization method, a melt polymerization method such as a transesterification method, a solution polymerization method, and an interfacial polymerization method. When the interfacial polymerization method is used, a solution (organic phase) obtained by dissolving a dicarboxylic acid chloride in an organic solvent immiscible with water is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic dihydroxy compound and a polymerization catalyst, and heated at 50°C. A method of carrying out the polymerization reaction with stirring at a temperature of 25° C. or less for 0.5 to 8 hours is preferably exemplified below.

As the solvent used for the organic phase, a solvent that dissolves the polyester resin of the present invention without being miscible with water is preferable. Examples of such solvents include chlorinated solvents such as methylene chloride, 1,2-dichloroethane, chloroform and chlorobenzene, and aromatic hydrocarbon solvents such as toluene, benzene and xylene, which are easy to use for production. Therefore, methylene chloride is preferred.

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

In the melt polymerization reaction, a dihydroxy compound and a dicarboxylic acid compound or a diester thereof are generally mixed and reacted at generally 120 to 350°C, preferably 150 to 300°C, more preferably 180 to 270°C. The degree of pressure reduction is changed step by step until finally 0.13 kPa or less to distill off the produced water and hydroxy compounds such as alcohol out of the system, and the reaction time is usually about 1 to 10 hours.

In addition, a transesterification catalyst and a polymerization catalyst can be used to speed up the polymerization rate in the melt process. As the transesterification catalyst, one known per se can be used, and for example, compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, and lead elements can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Among these, compounds such as oxides, acetates and alcoholates of manganese, magnesium, zinc, titanium and cobalt are preferred from the viewpoint of the melt stability and color of the thermoplastic resin and the small amount of polymer insoluble foreign matter. These compounds can be used in combination of two or more. As the polymerization catalyst, those known per se can be employed, and preferred examples include antimony compounds, titanium compounds, germanium compounds, tin compounds and aluminum compounds. Examples of such compounds include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates of antimony, titanium, germanium, tin and aluminum. Moreover, these compounds can be used in combination of two or more. Among these, tin, titanium and germanium compounds are preferred from the viewpoint of the melt stability and hue of the thermoplastic resin. The amount of the catalyst used is preferably in the range of 1×10 ⁻⁸ to 1×10 ⁻³ mol per 1 mol of the dicarboxylic acid compound.

A terminal blocking agent may be used in the polyester resin of the present invention in order to adjust the molecular weight and improve the thermal stability. Examples of terminal blocking agents include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, ketene imine compounds, and the like.

《Resin composition》
Additives such as release agents, heat stabilizers, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants, plasticizers and fillers may be added to the thermoplastic resin of the present invention as appropriate. can be used as a resin composition. As specific release agents and heat stabilizers, those described in International Publication No. 2011/010741 are preferred.

Particularly preferred release agents include monoglyceride stearate, triglyceride stearate, pentaerythritol tetrastearate, and a mixture of triglyceride stearate and stearyl stearate. The amount of the ester in the release agent is preferably 90% by weight or more, more preferably 95% by weight or more, when the release agent is taken as 100% by weight. In addition, the release agent to be blended in the thermoplastic resin is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, based on 100 parts by weight of the thermoplastic resin. Preferably, the range of 0.02 to 0.5 parts by weight is more preferable.

Heat stabilizers include phosphorus heat stabilizers, sulfur heat stabilizers and hindered phenol heat stabilizers.

Particularly preferred phosphorus-based heat stabilizers include tris(2,4-di-tert-butylphenyl)phosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. Phyto, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite is used. The content of the phosphorus-based heat stabilizer in the polycarbonate thermoplastic resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

A particularly preferred sulfur-based heat stabilizer is pentaerythritol-tetrakis(3-laurylthiopropionate). Moreover, the content of the sulfur-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Preferred hindered phenol heat stabilizers include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propionate].

The content of the hindered phenol-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

A phosphorus-based heat stabilizer and a hindered phenol-based heat stabilizer can also be used in combination.

As the ultraviolet absorber, at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. is preferred.

In the benzotriazole-based UV absorber, more preferably 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazol-2-yl)phenol].

Benzophenone UV absorbers include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Triazine-based UV absorbers 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.

2,2'-p-phenylenebis(3,1-benzoxazin-4-one) is particularly suitable as the cyclic imino ester-based ultraviolet absorber.

As the cyanoacrylate ultraviolet absorber, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenyl acryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like.

The amount of the ultraviolet absorbent compounded is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. It is possible to give sufficient weather resistance to

"lens"
The thermoplastic resin of the present invention or the resin composition containing it as described above is suitable for optical lenses, particularly imaging lenses.

When the optical lens is produced by injection molding, it is preferable to perform molding under the conditions of a cylinder temperature of 230 to 350°C and a mold temperature of 70 to 180°C. More preferably, molding is carried out under the conditions of a cylinder temperature of 250 to 300°C and a mold temperature of 80 to 170°C. If the cylinder temperature is higher than 350°C, the thermoplastic resin will decompose and color. Moreover, when the mold temperature is higher than 180° C., it tends to be difficult to remove the molded piece made of the thermoplastic resin from the mold. On the other hand, if the mold temperature is less than 70° C., the resin will harden too quickly in the mold during molding, making it difficult to control the shape of the molded piece, and the mold applied to the mold will not be sufficiently transferred. is likely to be difficult.

The optical lens of the present invention is preferably implemented in the form of an aspherical lens if necessary. Aspherical lenses can eliminate spherical aberration with a single lens, so there is no need to combine multiple spherical lenses to remove spherical aberration, which helps reduce weight and molding costs. be possible. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.

Moreover, the thermoplastic resin of the present invention is particularly useful as a material for optical lenses that are thin, small, and have a complicated shape, because of its high molding fluidity. As a specific lens size, the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, further preferably 0.1 to 2.0 mm. Also, the diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, still more preferably 3.0 to 10.0 mm. In addition, it is preferable that the lens is a meniscus lens having a convex surface on one side and a concave surface on the other side.

The lens made of the thermoplastic resin of the present invention can be molded by any method such as mold molding, cutting, polishing, laser processing, electrical discharge machining, and etching. Among these, mold molding is more preferable from the viewpoint of manufacturing cost.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited thereto.

"Evaluation method"
(1) Cis isomer ratio (NMR)
It was measured by ¹ H NMR of JNM-ECZ400S/L1 manufactured by JEOL Ltd., and the cis isomer ratio (molar ratio) of TMCBD was calculated.
50 mg of sample
Solvent deuterated dimethyl sulfoxide 0.6 mL
Accumulated times: 512 times

(2) Amount of tertiary amine Triethylamine in TMCBD was quantified using the following equipment and conditions. For quantification, a calibration curve was created using an aqueous solution of triethylamine having a predetermined concentration.
Ion chromatography device: Dionex ICS-2000,
Cation measurement column: Dionex IonPac CS17 (30 ° C.)
Eluent: 5 mmol/L methanesulfonic acid Flow rate: 1.0 mL/min Detector: Electrical conductivity (using auto suppressor)
Amount of sample introduced: 100 μL

(3) Boric acid content Boric acid in TMCBD was quantified using the following equipment and conditions. For quantification, a calibration curve was created using an aqueous solution of boric acid having a predetermined concentration.
GC-MS analyzer: Agilent GC6890N, MSD5975B
Column: Agilent 19091S-433 HP-5MS
Measurement conditions: flow rate 1 mL/min, column oven 50 to 310° C., measurement time 60 minutes Silylation method: 10 mg of sample is dissolved in acetonitrile, 0.1 mL of pyridine and 0.1 mL of BSTFA (silylating agent) are added, and filtered. Inject 1 μL into the device after filtration

(4) Composition ratio ¹ H NMR spectrum at room temperature was measured using JNM-ECZ400S/L1 (resonance frequency 400 MHz) manufactured by JEOL Ltd., and the signal intensity ratio based on the structural unit derived from each dihydroxy compound showed that the heat A composition ratio of each structural unit in the plastic resin was calculated.
Thermoplastic resin amount 40 mg
Solvent deuterated chloroform 0.6 mL

(5) Content of Phenol in Thermoplastic Resin After dissolving 1.25 g of thermoplastic resin in 7 mL of methylene chloride, reprecipitation was performed by adding acetone so that the total amount was 25 mL. Then, the treated liquid was filtered through a 0.2 μm membrane filter and quantified by liquid chromatography.

(6) Terminal phenyl group concentration ¹ H NMR was measured in the same manner as in the measurement of the thermoplastic resin composition ratio above, and the terminal phenyl group concentration was measured using 1,1,2,2-tetrabromoethane as an internal standard. It was obtained from the signal intensity ratio based on the target and the terminal phenyl group.

(7) Viscosity Average Molecular Weight The viscosity average molecular weight of the thermoplastic resin was measured by the following method. From a solution of 0.7 g of thermoplastic resin dissolved in 100 ml of methylene chloride, the specific viscosity (η _sp ) of the solution at 20° C. was measured. And Mv calculated by the following formula was made into the viscosity average molecular weight.
η _sp /c=[η]+0.45×[η] ² c
[η]=1.23×10 ⁻⁴ Mv ^0.83
η _sp : Specific viscosity η: Intrinsic viscosity c: 0.7
Mv: viscosity average molecular weight

(8) Glass transition temperature The glass transition temperature of the resin composition is measured using a thermal analysis system DSC-2910 manufactured by TA Instruments, under a nitrogen atmosphere according to JIS K7121 (nitrogen flow rate: 40 ml / min), heating rate : Measured under the condition of 20°C/min.

(9) Initial hue The thermoplastic resin pellets are dried at 100 ° C. for 12 hours, supplied to an injection molding machine (EC100NII-2Y manufactured by Toshiba Machine Co., Ltd.), and molded at a resin temperature of 260 ° C. and a mold temperature of 80 ° C. ( 100 mm width x 100 mm width x 3 mm thickness) was molded. The initial hue (YI ₀ ) of the molded plate was measured according to JIS K7373 with SE-2000 (C light source, viewing angle 2°) manufactured by Nippon Denshoku Kogyo Co., Ltd.

(10) Spectral light transmittance (320 nm, 350 nm)
The light transmittance of the molded plate (thickness: 3 mm) was measured using a UV-visible spectrophotometer (Hitachi High-Technologies Corporation U4100).

(11) Hue and color difference after weather resistance test Using a super xenon weather meter manufactured by Suga Test Instruments Co., Ltd., the above molded plate is left to stand for 1000 hours under conditions of 63 ° C. and 50% relative humidity, and the hue of the molded plate (YI ₁ ) was measured according to JIS K7373 with SE-2000 (C light source, viewing angle 2°) manufactured by Nippon Denshoku Kogyo Co., Ltd., and the color difference (ΔYI=YI ₁ -YI ₀ ) was calculated.

(12) Refractive index (n _D ) and Abbe number 3 g of a thermoplastic resin was dissolved in 50 ml of methylene chloride and cast on a glass petri dish to prepare a film. After sufficiently drying at room temperature, it was dried at 120° C. for 8 hours to produce a film with a thickness of about 100 μm.

Using an ATAGO DR-M2 Abbe refractometer, the refractive index (wavelength: 589 nm) and Abbe number (wavelength: 486 nm, 589 nm, calculated using the following formula from the refractive index at 656 nm) at 25 ° C. were measured. did.
ν=(n _D −1)/(n _F −n _C )
In addition, in this specification,
n _D : refractive index at a wavelength of 589 nm;
n _C : refractive index at a wavelength of 656 nm;
n _F : Refractive index at a wavelength of 486 nm.

(13) Absolute value of orientation birefringence (|Δn|)
A cast film having a thickness of 100 μm prepared by the above method is stretched twice at Tg + 10 ° C., and the phase difference (Re) at 589 nm is measured using an ellipsometer M-220 manufactured by JASCO Corporation. The absolute value of birefringence was obtained.
|Δn|=|Re/d|
Δn: orientation birefringence
Re: phase difference (nm)
d: thickness (nm)

(14) Optical distortion: Optical distortion was evaluated by sandwiching an aspherical lens molded by the method described in the manufacturing example between two polarizing plates and visually observing light leakage from behind by the crossed Nicols method. Evaluation was performed according to the following three-level criteria.
・Almost no light leakage ・Slight light leakage is observed ・Light leakage is noticeable

《Manufacturing example》
(Preparation of TMCBD)
The TMCBD used in each example was prepared as follows to reduce impurities. The raw material TMCBD was purchased from FUJIFILM Wako Pure Chemical. The TMCBD had a cis isomer ratio of 60 mol %, a boric acid content of 250 ppm by weight, and a triethylamine content of 1350 ppm.
After dissolving TMCBD in toluene, the washing water was separated using ion-exchanged water at 40° C. when the pH of the washing water reached 7-8. Toluene was completely distilled off from the obtained toluene solution to obtain a white powder, which was vacuum-dried at 80° C. for 48 hours. The resulting TMCBD had a cis isomer ratio of 60 mol %, a boric acid content of 80 weight ppm, and a triethylamine content of 1350 weight ppm. Subsequently, after dissolving in toluene, it was washed twice with a 1% hydrochloric acid aqueous solution, and then washed with deionized water. When the pH of the washing water reached 7-8, toluene was completely distilled off. The resulting white powder was vacuum dried at 80° C. for 48 hours. The finally obtained TMCBD had a cis isomer ratio of 60 mol %, a boric acid content of 80 weight ppm, and a triethylamine content of 350 weight ppm.

<Example 1>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter abbreviated as TMC) 259 parts by weight, TMCBD (cis isomer ratio 60 mol%, boric acid content 80 ppm by weight, triethylamine content 350 ppm by weight) 360 parts by weight, diphenyl carbonate (hereinafter abbreviated as DPC) 714 parts by weight, and tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) 9.1 × 10 ^-2 parts by weight as a catalyst and lithium acetate 5.8 parts ×10 ⁻² parts by weight was heated to 180° C. under a nitrogen atmosphere and melted.

After that, the temperature was raised to 240° C. over 2 hours, and the pressure inside the reactor was reduced from 101.3 kPa to 13.4 kPa over 40 minutes while distilling off the by-product phenol. Subsequently, the pressure in the reactor was maintained at 13.4 kPa, and transesterification was carried out for 80 minutes while further distilling off phenol. The internal pressure was reduced from 13.4 kPa to 2 kPa in terms of absolute pressure, and the temperature was further raised to 260° C. to remove distilled phenol out of the system. After that, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. The polycondensation reaction was terminated when a predetermined stirring power was achieved. The nitrogen was discharged from the bottom of the reaction tank under pressure, and the mixture was cut with a pelletizer while being cooled in a water tank to obtain pellets. Various evaluations were performed on the pellets, and the evaluation results are shown in Table 1.

0.05% by weight of tris(2,4-di-tert-butylphenyl)phosphite and 0.10% by weight of glycerin monostearate were added based on the weight of the resin, and a vented φ15 mm twin-screw extruder was used. and pelletized. After drying the pellets at 120° C. for 4 hours, they were injection molded at a cylinder temperature of 280° C. and a mold temperature of 130° C. to obtain a lens having a thickness of 0.3 mm, a convex radius of curvature of 5 mm and a concave radius of curvature of 4 mm. The resulting aspherical lens was sandwiched between two polarizing plates, and the optical distortion was evaluated by visual observation of light leakage from the rear by the crossed Nicols method.

<Examples 2 and 3>
Polycarbonates of Examples 2 and 3 were obtained in the same manner as in Example 1, except that the amounts of TMC and TMCBD were changed.

<Example 4>
Instead of 259 parts by weight of TMC and 360 parts by weight of TMCBD, 308 parts by weight of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (hereinafter abbreviated as SBI) and 336 parts by weight of TMCBD A polycarbonate was obtained in the same manner as in Example 1, except that the was used. When optical distortion was evaluated by the same method as in Example 1, almost no light leakage was observed.

<Examples 5 and 6>
Polycarbonates of Examples 5 and 6 were obtained in the same manner as in Example 4, except that the amounts of SBI and TMCBD were changed.

<Example 7>
Example 1 except that 252 parts by weight of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as BCF) and 384 parts by weight of TMCBD were used instead of 259 parts by weight of TMC and 360 parts by weight of TMCBD. Polycarbonate was obtained in the same manner as. When optical distortion was evaluated by the same method as in Example 1, almost no light leakage was observed.

<Examples 8 and 9>
Polycarbonates of Examples 8 and 9 were obtained in the same manner as in Example 7, except that the amounts of BCF and TMCBD were changed.

<Example 10>
Same as Example 1 except that 459 parts by weight of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter abbreviated as BPAF) and 283 parts by weight of TMCBD were used instead of 259 parts by weight of TMC and 360 parts by weight of TMCBD. to obtain a polycarbonate. When the optical distortion was evaluated by the same method as in Example 1, a slight light leakage was observed.

<Examples 11 and 12>
Polycarbonates of Examples 11 and 12 were obtained in the same manner as in Example 10, except that the amounts of BPAF and TMCBD were changed.

<Example 13>
A ^polyester A carbonate was obtained. When the optical distortion was evaluated by the same method as in Example 1, a slight light leakage was observed.

<Examples 14 to 16>
Polyester carbonates of Examples 14, 15, and 16 were obtained in the same manner as in Example 13, except that the dihydroxy compound and the amount were changed.

<Example 17>
A polycarbonate was obtained in the same manner as in Example 1 except that the amounts were changed to 83 parts by weight of TMC and 350 parts by weight of TMCBD instead of 259 parts by weight of TMC and 360 parts by weight of TMCBD, and 213 parts by weight of BPAF was used. When the optical distortion was evaluated by the same method as in Example 1, a slight light leakage was observed.

"result"
The results for polycarbonate are summarized in Table 1 below.

Results for the polyester carbonates are summarized in Table 2 below.

Data relating to the refractive index, etc. of various polymers are summarized in Table 3 below.

The refractive index and Abbe number of various polymers described in Examples 1-17 and Table 3 are plotted in FIG.

For various prior _art homopolymers other than TMCBD homopolymers, as shown in FIG. It can be seen that the relationship satisfies B):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (B)

It is known that when these polycarbonate-constituting monomers are copolymerized at a weight ratio of 1:1, the refractive index and Abbe number are roughly intermediate values between those of homopolymers. It is Therefore, in the resin of the prior art, the refractive index (n _D ) and the Abbe number (ν) satisfy the relationship of the above equation (B) indicated by the "limiting line of the prior art".

On the other hand, it can be seen that the copolymer containing TMCBD of the present invention does not satisfy the formula (B), but the following formula (A):
n _D <1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (A)

The thermoplastic resins of Examples 1 to 17 were excellent in hue, low in birefringence, and excellent in heat resistance and moldability as lens resins. Further, since the thermoplastic resins of Examples 1 to 17 substantially do not contain heterocyclic amine, it can be said that the hue is excellent in this respect as well.

Claims (13)

A first structural unit derived from a dihydroxy compound represented by the following formula (1):

(wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, or carbon atoms an aralkyloxy group of numbers 7 to 20, or a halogen atom; a cyclobutane ring indicates either a cis/trans isomer mixture, a cis isomer alone, or a trans isomer alone);
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (TMC), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), or 6,6′-dihydroxy- and a second structural unit derived from 3,3,3′,3′-tetramethylspirobiindane (SBI) ,
Thermal lens for lenses, which is polycarbonate or polyester carbonate , containing more than 50 mol % and 95 mol % or less of the first structural unit, and having a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (A): Plastic resin:
n _D <1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.853 (A) The thermoplastic resin according to claim 1, further comprising a terminal aromatic group derived from a diester carbonate represented by the following formula (2):

(wherein R ₅ and R ₆ are each independently a substituted or unsubstituted aromatic group). The thermoplastic resin according to claim 1 or 2 , having a refractive index (n _D ) of more than 1.470 and not more than 1.600. The thermoplastic resin according to any one of claims 1 to 3 , which has an Abbe number (ν) in the range of 25 or more and 50 or less. The thermoplastic resin according to any one of claims 1 to 4 , having a refractive index (n _D ) and an Abbe number (ν) that satisfy the following formula (C):
n _D ≧1.156×10 ⁻⁴ ×ν ² −1.289×10 ⁻² ×ν+1.800 (C) The thermoplastic resin according to any one of claims 1 to 5 , having a glass transition temperature in the range of 130°C to 170°C. The heat according to any one of claims 1 to 6 , wherein the initial hue (YI ₀ ) measured according to JIS K7373 on a molded plate of 100 mm long × 100 mm wide × 3 mm thick is 4.0 or less. plastic resin. Thermoplastic resin according to any one of claims 1 to 7 , which is substantially free of heterocyclic amines. transesterifying a dihydroxy compound that provides the first structural unit, a dihydroxy compound that provides the second structural unit, and a diester carbonate in the presence of an alkali metal catalyst and/or an alkaline earth metal catalyst; A method for producing a thermoplastic resin according to any one of claims 1 to 8 . a dihydroxy compound providing the first structural unit, a dicarboxylic acid compound providing the second structural unit, and a carbonic acid diester are esterified in the presence of a titanium compound catalyst or in the presence of an aluminum catalyst and a phosphorus compound catalyst; / Or the method for producing a thermoplastic resin according to any one of claims 1 to 8 , characterized by performing an ester exchange reaction. The method for producing a thermoplastic resin according to claim 9 or 10 , wherein the dihydroxy compound that provides the first structural unit has a tertiary amine content of 1000 ppm by weight or less. The method for producing a thermoplastic resin according to any one of claims 9 to 11 , wherein the dihydroxy compound that provides the first structural unit has a boric acid content of 100 ppm by weight or less. An optical lens comprising the thermoplastic resin according to any one of claims 1 to 8 .

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