JPWO2020122122A1 - Thermoplastic resin for lenses and lenses containing them - Google Patents

Abstract

The present invention provides a thermoplastic resin for a lens that can give a range of lens types so that an imaging lens designer can adopt various types of lenses. The thermoplastic resin for a lens of the present invention has a first structural unit derived from a dihydroxy compound represented by the following formula (1): (In the formula, R1, R2, R3, and R4 are independent of each other. Hydrogen atom, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, 6 to 6 carbon atoms Shows 10 aryl groups, aralkyl groups with 7 to 20 carbon atoms, aryloxy groups with 6 to 10 carbon atoms or aralkyloxy groups with 7 to 20 carbon atoms, or halogen atoms; cyclobutane rings are cis-trans isomers. (Indicates either a body mixture, cis isomer alone, or trans isomer alone); a refractive index having a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound and satisfying the following formula (A). It has nD) and the number of Abbe (ν): nD <1.156 × 10-4 × ν2-1.289 × 10-2 × ν + 1.853 (A)

Description

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

Plastic imaging lenses used in devices such as smartphones are strongly required to have low birefringence and improved aberration correction capability. Conventionally, in such an imaging lens, aberration correction is performed by a combination of a plurality of lenses having different optical characteristics (refractive index, Abbe number) and a combination of lens shapes.

For example, as a resin having a high refractive index and a low Abbe number for an imaging lens, Patent Document 1 discloses a polycarbonate using a specific monomer without using bisphenol A as a raw material.

Polycarbonates using 2,2,4,4-tetramethyl-1,3-cyclobutanediol (hereinafter referred to as TMCBD) as a monomer have been conventionally known (Patent Documents 2 to 6 and Non-Patent Document 1). ). Further, 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.

International Publication No. 2017/010318 Special Publication No. 38-26798 Japanese Unexamined Patent Publication No. 63-92644 Japanese Unexamined Patent Publication No. 2-22416 Japanese Unexamined Patent Publication No. 11-240945 Japanese Unexamined Patent Publication No. 2015-137355 Special Table No. 8-506341 Gazette

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 should one lens have depends on the refractive index and Abbe number of other lenses, and therefore cannot be unconditionally defined.

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

Therefore, even if the designer of the 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.

Further, even if a resin capable of providing a specific refractive index and a specific Abbe number exists, other characteristics such as hue, heat resistance, moldability, and water absorption rate are not suitable as a resin for an imaging lens. In that respect as well, there are restrictions on the lenses that can be adopted by the designer of the imaging lens.

Therefore, an object of the present invention is to provide a thermoplastic resin for a lens that can give a width to the type of lens so that a designer of an imaging lens 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 present inventors have found that the above problems can be solved by the present invention having the following aspects.
<< Aspect 1 >>
With the first structural unit derived from the dihydroxy compound represented by the following formula (1):

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 to 10 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 6 to 10 carbon atoms aryl groups, 7 to 20 carbon atoms aralkyl groups, 6 to 10 carbon atoms aryloxy groups or carbon atoms It shows the aralkyloxy group of the number 7 to 20 or a halogen atom; the cyclobutane ring indicates either a cis-trans isomer mixture, a cis isomer alone, or a trans isomer alone);
It has a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound, and has a refractive index (n _D ) and an Abbe number (ν) that satisfy the following mathematical formula (A).
Thermoplastic resin 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 embodiment 1, further comprising a terminal aromatic group derived from a carbonic acid diester represented by the following formula (2):

(In the formula, R ₅ and R ₆ are independently substituted or unsubstituted aromatic groups, respectively).
<< Aspect 3 >>
The second structural unit is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, a heterocyclic dihydroxy compound and an aromatic dihydroxy compound, and an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and a heterocyclic dicarboxylic acid compound. The thermoplastic resin according to aspect 1 or 2, which is derived from at least one compound selected from the group consisting of an aromatic dicarboxylic acid compound.
<< Aspect 4 >>
The thermoplastic resin according to any one of aspects 1 to 3, wherein the first structural unit is contained in an amount of more than 50 mol% and 95 mol% or less.
<< Aspect 5 >>
The thermoplastic resin according to any one of aspects 1 to 4, wherein the refractive index (n _{D) is more than 1.470 and 1.600 or less.}
<< Aspect 6 >>
The thermoplastic resin according to any one of aspects 1 to 5, wherein the Abbe number (ν) is 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, wherein the glass transition temperature is 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 in accordance with JIS K7373 for a molded plate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm is 4.0 or less. resin.
<< Aspect 10 >>
The thermoplastic resin according to any one of aspects 1 to 9, which is substantially free of heterocyclic amines.
<< Aspect 11 >>
The thermoplastic resin according to any one of aspects 1 to 10, which is polycarbonate or polyester carbonate.
<< Aspect 12 >>
Transesterification of the dihydroxy compound that brings about the first structural unit, the dihydroxy compound that brings about the second structural unit, and the carbonate diester in the presence of an alkali metal catalyst and / or an alkaline earth metal catalyst. The method for producing a thermoplastic resin according to any one of aspects 1 to 11, which is characteristic.
<< Aspect 13 >>
The dihydroxy compound that yields the first structural unit, the dicarboxylic acid compound that yields the second structural unit, and the carbonic acid diester are esterified in the presence of a titanium compound catalyst or in the presence of an aluminum and phosphorus compound catalyst. / Or The method for producing a thermoplastic resin according to any one of aspects 1 to 11, wherein the ester exchange reaction is carried out.
<< Aspect 14 >>
The method for producing a thermoplastic resin according to aspect 12 or 13, wherein the tertiary amine content of the dihydroxy compound that provides the first structural unit is 1000 ppm by weight or less.
<< Aspect 15 >>
The method for producing a thermoplastic resin according to any one of aspects 12 to 14, wherein the boric acid content of the dihydroxy compound that brings about the first structural unit is 100 ppm by weight or less.
<< Aspect 16 >>
An optical lens comprising the thermoplastic resin according to any one of aspects 1 to 11.

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

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 the formula (1) described later, but is at least one selected from the group consisting of polycarbonate, polyester carbonate, and polyester. This is preferable from the viewpoint of the effect of the present invention, and it is particularly preferable that it is composed of polycarbonate or polyester carbonate. The present invention also relates to the use or method of using a thermoplastic resin for a lens as described below.

（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 a lens of the present invention has a first structural unit derived from a dihydroxy compound represented by the following formula (1):

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 to 10 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 6 to 10 carbon atoms aryl groups, 7 to 20 carbon atoms aralkyl groups, 6 to 10 carbon atoms aryloxy groups or carbon atoms It shows the aralkyloxy group of the number 7 to 20 or a halogen atom; the cyclobutane ring indicates either a cis-trans isomer mixture, a cis isomer alone, or a trans isomer alone);
It has a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound, and has 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 the conventional resin, the refractive index (n _D ) and the Abbe number (ν) have a relationship that satisfies the following mathematical formula (B):
n _D ≧ 1.156 × 10 ^-4 × ν ^{2 −} 1.289 × 10 ^-2 × ν + 1.853 (B)

On the other hand, the present inventors have found that when the thermoplastic resin contains the repeating unit of the formula (1), the relationship between the refractive index and the Abbe number becomes specific from the conventional relationship. Specifically, it has been found that when the thermoplastic resin contains the repeating unit of the formula (1), the Abbe number tends to be smaller for a specific refractive index than in the past.

The presence of a resin having such a relationship of refractive index and Abbe number gives the designer of an imaging lens a great advantage in lens design because it allows various types of lenses to be adopted. .. It was also found that the thermoplastic resin containing the repeating unit of the formula (1) is also advantageous in the properties required for the lens such as hue, moldability, heat resistance, and water absorption.

Conventionally, polycarbonate and its refractive index have been known as thermoplastic resins using TMCBD as a monomer, but it has not been known that such polycarbonate has a specifically low Abbe number. Therefore, it was not known that such polycarbonate would be useful in lens design.

The reason why the thermoplastic resin of the present invention expresses such a refractive index and Abbe number is not bound by theory, but the thermoplastic resin containing the repeating unit of the 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.

In the present specification, the "refractive index (n _D )" is a refractive index measured at 25 ° C. and having a wavelength of 589 nm, and is measured by the method described in Examples.

_{The refractive index (n D} ) of the thermoplastic resin of the present invention is in the range of more than 1.470 and less than 1.600. The refractive index (n _D ) may be 1.475 or more, 1.480 or more, 1.485 or more, 1.490 or more, 1.495 or more, or 1.500 or more, and 1.590 or less, 1 It may be .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.

In the present specification, the "Abbe number (ν)" is calculated from the refractive indexes of wavelengths 486 nm, 589 nm, and 656 nm measured at 25 ° C. using the following formula, and these are measured by the method described in Examples:
ν = (n _D -1) / (n _F −n _C )
(Here, n _D : the refractive index at a wavelength of 589 nm, n _C : a refractive index at a wavelength of 656 nm, n _F : a 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, and 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, and may be 30 or more and 42 or less.

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

Further, the thermoplastic resin in the present invention may have a refractive index (n _D ) and an Abbe number (ν) satisfying the following mathematical formula (E):
n _D <1.156 × 10 ^-4 × ν ^{2 −} 1.289 × 10 ^-2 × ν + β (E)
Here, 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 Examples. It may be ℃ or less, or 150 ℃ or less. 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 15,000 or more, 18,000 or more, or 20,000 or more, and 30,000 or less, 25,000 or less, or 22,000 or less when measured by the method described in Examples. You may. For example, the viscosity average molecular weight of the thermoplastic resin of the present invention may be 15,000 or more and 30,000 or less or 18,000 or more and 22,000 or less.

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, and 5. It is preferably 0 × 10 ^-3 or less, or 3.0 × 10 ^{-3 or less.} Within such a range, the optical distortion becomes 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, still more preferably 45% or more at a wavelength of 320 nm when measured by the method described in 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 when measured by the method described in Examples. Especially 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 shall be 10.0 or less, 8.0 or less, 7.0 or less, or 6.0 or less when measured by the method described in Examples. Is preferable.

_{The hue (YI 1} ) of the thermoplastic resin in the present invention after the 1000-hour weather resistance test was 13.0 or less, 12.0 or less, 10.0 or less, 9. It is preferably 0 or less, or 8.0 or less. 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 the first structural unit in an amount of more than 50 mol% and 95 mol% or less from the viewpoint of obtaining suitable physical properties as a resin for lenses. 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 a thermoplastic resin. For example, the first structural unit may be 60 mol% or more and 90 mol% or less, and 70 mol% or more and 90 mol% or less. The composition ratio of the structural unit can be measured by ^{1 H NMR method.}

The thermoplastic resin in the present invention preferably contains a second structural unit in an amount of 5 mol% or more and less than 50 mol% from the viewpoint of obtaining suitable physical properties as a resin for a lens. The second structural unit may be 10 mol% or more, or 15 mol% or more, 20 mol% or more, or 25 mol% or more, and may be 45 mol% or less, 40 mol% or less, 30 mol% or less, 25 mol% or less, or 20 mol% or less. It 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 the structural unit can be measured by ^{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 description of "structural unit derived from a dihydroxy compound" is a structural unit of a portion of the dihydroxy compound excluding the dihydroxy group as long as the thermoplastic resin can provide the advantageous effect of the present invention. To 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" is defined in the thermoplastic resin brought about by the dihydroxy compound. It means the portion of the repeating unit of the above excluding the two ester bonds. The same interpretation applies to "structural units derived from dicarboxylic acid compounds".

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

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

When the first structural unit _{is represented by A 1} and the second structural unit _{is represented by A 2} , the thermoplastic resin of the present invention contains-(X-A ₁ )-,-(X-A ₂ )-, and /. Or-(X-A _1- X-A ₂ )-includes a repeating unit. 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, for example, a dihydroxy compound having the following first structural unit, and a dihydroxy compound having the following second structural unit and a carbonate precursor. Obtained by reacting with the body. In particular, the polycarbonate in the present invention obtained by transesterification with a carbonic acid diester has an excellent hue because it does not contain pyridine or an acid chloride thereof as compared with a polycarbonate obtained by using phosgene or the like with pyridine as a catalyst. ing. Therefore, it is preferable that the polycarbonate in the present invention contains substantially no pyridine. For example, pyridine or its acid chloride is ^{determined by 1} H NMR and determined from the signal intensity ratio based on the internal standard and pyridine or its acid chloride, using 1,1,2,2-tetrabromoethane as the internal standard. It can be 500 ppm or less, 100 ppm or less, or 50 ppm 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 brings about the first structural unit>
The polycarbonate in the present invention has a first structural unit derived from the dihydroxy compound represented by the following formula (1):

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 to 10 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 6 to 10 carbon atoms aryl groups, 7 to 20 carbon atoms aralkyl groups, 6 to 10 carbon atoms aryloxy groups, carbon atoms It shows an aralkyloxy group of number 7 to 20 or a halogen atom; the cyclobutane ring indicates either a cis-trans isomer mixture, a cis isomer alone, or a trans isomer alone).

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

Examples of the dihydroxy compound represented by the formula (1) include 2-methyl-1,3-cyclobutanediol, 2,4-dimethyl-1,3-cyclobutanediol, and 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 can be mentioned. The most suitable 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 the formula (1) is preferably a cis-trans isomer mixture. The ratio is not limited, but the lower limit of the cis isomer ratio is preferably 30 mol% or more, more preferably 45 mol% or more, still 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, still more preferably 80 mol% or less. When the cis isomer is in such a range, the moldability of the polymer tends to be good. The cis isomer ratio can be measured by ^{1 H NMR method.}

In order to produce a dihydroxy compound containing a cyclobutane ring represented by the formula (1), diketen is produced by addition or dimerization of ketene represented by the following formula (10), and then cyclobutane is added by hydrogenation. A ring-containing dihydroxy compound 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 the formula (10), R ₁₉ and R ₂₀ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 20 carbon atoms. , Cycloalkoxy group with 6 to 20 carbon atoms, aryl group with 6 to 10 carbon atoms, aralkyl group with 7 to 20 carbon atoms, aryloxy group with 6 to 10 carbon atoms, 7 to 20 carbon atoms Indicates an aryloxy group or a halogen atom.)

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

Synthesis example (I) is a method of producing by using isobutyric acid as a starting material, advancing the addition or dimerization reaction of dimethylketene produced by thermal decomposition, and then hydrogenating. Here, using isobutyric anhydride or isobutyric acid as a raw material is an industrially advantageous method, and the details are described in Patent Document 7.

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

When the dihydroxy compound that brings about the first structural unit obtained by such a production method is used as the monomer of the thermoplastic resin, the present inventors use the tertiary amine remaining in the dihydroxy compound as the monomer of the thermoplastic resin. It has been found to adversely affect hue and transparency. Even if a quaternary amine such as tetramethylammonium hydroxide is used as the polymerization catalyst, there are many tertiary amines remaining in the dihydroxy compound that brings the first structural unit, although the hue does not deteriorate. In some cases, it was unexpected that the hue of the polymer would deteriorate.

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

Further, as other methods for producing dimethyl ketene, a method by decarboxylation of dimethyl malonic anhydride, a method by thermal decomposition of N-isobutyryl phthalimide, α-carbomethoxy-α, β-dimethyl-β-butyrolactone Examples thereof include a method by thermal decomposition of dimethylketene dimer and a method by thermal decomposition of dimethylketene dimer.

As a method for adding hydrogen to the cyclic diketone after the addition or dimerization reaction of dimethyl ketene, a method using a metal hydride and a method in which hydrogen gas is allowed to act 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. In industrial use, a boron-based reducing agent is suitable because of the stability and handleability of the compound, and sodium borohydride is often used as the reducing agent. It is characterized in that boric acid is produced as a by-product in the hydrogenation reaction using a boron-based reducing agent.

When the dihydroxy compound that brings about the first structural unit obtained by such a production method is used as a monomer of the thermoplastic resin, the present inventors, the boric acid remaining in the dihydroxy compound is the hue of the thermoplastic resin and the color of the thermoplastic resin. We have found that it adversely affects transparency.

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

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

For example, as the dihydroxy compound that brings about the second structural unit, a linear or cyclic, substituted or unsubstituted hydrocarbon-based dihydroxy compound that may have a hetero atom and / or may be branched. In particular, it may be a hydrocarbon-based dihydroxy compound having 2 to 50 carbon atoms.

Specifically, examples of the dihydroxy compound that brings about the second structural unit include an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, a heterocyclic dihydroxy compound, and an aromatic dihydroxy compound, and in particular, International Publication No. 2004 Examples thereof include dihydroxy compounds having oxyalkylene glycols such as dihydroxy compounds, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol as described in Pamphlet No. / 111106 and Pamphlet No. 2011/021720. 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 an aliphatic dihydroxy compound having a linear or branched chain 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 equation (3), m indicates an integer of 2 to 12)

Specific examples of the aliphatic dihydroxy compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonane. Didiol, 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-hexaneglycol, 1,2-octylglycol, 2 -Eethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol And so on.

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

Examples of the heterocyclic dihydroxy compound include a monocyclic, polycyclic or condensed polycyclic dihydroxy compound having 3 to 30 carbon atoms, which may have a substituent. Specific examples of the heterocyclic dihydroxy compound include 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, isosorbide, and isomannide. , Isosorbide and the like. Isosorbide is preferable.

Examples of the aromatic dihydroxy compound 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 a bond of any of the following formulas (9). X and Y are independently integers of 0 or 1 to 4, and R ₇ and R ₈ are independently halogen atoms, alkyl groups having 1 to 10 carbon atoms, and 1 carbon atom. Alkoxy group of 10 to 10, cycloalkyl group of 6 to 20 carbon atoms, cycloalkoxy group of 6 to 20 carbon atoms, aryl group of 6 to 10 carbon atoms, aralkyl group of 7 to 20 carbon atoms, carbon atom Represents an organic residue selected from the group consisting of an aryloxy group of number 6 to 10 and an alkoxy group having 7 to 20 carbon atoms. L ₁ and L ₂ are independently divalent linking groups (eg, each). , Methylene group), and o and p independently indicate 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 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 the plurality of R ₁₅ and R ₁₆ are independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms, respectively. 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 for deriving the structural unit in which W is a single bond in the above formula (4) include 4,4'-biphenol and 4,4'-bis (2,6-dimethyl) diphenol. Be done.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (5) are α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene and α, α'-bis (4-hydroxyphenyl). ) -M-Diisopropylbenzene (usually referred to as "bisphenol M"), α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene and the like. It is preferably bisphenol M.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (6) are 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 (usually referred to as "BPEF"), 9,9-bis (4- (Hydroxyethoxy) -3-phenylphenyl) fluorene and the like can be mentioned. It is preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

Specific examples of the dihydroxy compound in which W is the structural unit of the formula (7) are 1,1-bis (4-hydroxyphenyl) cyclohexane (usually referred to as "bisphenol Z") and 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 (usually referred to as "bisphenol 3MZ"), 1, Examples thereof include 1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. Preferably 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3 methylphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -3,3,5- It is trimethylcyclohexane.

Specific examples of the dihydroxy compound for which W is the structural unit of the formula (8) are 4,4'-dihydroxydiphenylmethane, 2,4'-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, and 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 (usually "bisphenol A" , 2,2-bis (4-hydroxy-3-methylphenyl) propane (usually 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-4-4) 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- Examples thereof include hydroxyphenyl) decane and 1,1-bis (2,3-dimethyl-4-hydroxyphenyl) decane. Preferred are bisphenol A, bisphenol C, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 1,1-bis (4-hydroxyphenyl) decane.

Specific examples of the dihydroxy compound for deriving a structural unit in which W is any of the formula (9) are 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyle. -Tel, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 3,3'-dimethyl-4,4' Examples thereof include −dihydroxydiphenylsulfide and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone. Preferably, it is 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfide and 4,4'-dihydroxydiphenylsulfide.

Among the above divalent phenols, the formula (5) is bisphenol M, the formula (6) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and the formula (7) is 1,1-bis (4-). Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3 methylphenyl) 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 3,3'-dimethyl-4,4'-dihydroxy in formula (9) Diphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide is preferable. Preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) ) Hexafluoropropane.

Further, as the divalent phenol derived to the structural unit other than the formula (4), 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'-Tetramethylspirobiindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- (4-hydroxyphenyl) -3-[ Examples thereof include 1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, and ethylene glycol bis (4-hydroxyphenyl) ether. Preferably, it 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. One of these compounds may be used alone, or two or more of these compounds may be used in combination.

The dihydroxy compounds that provide the second structural unit are 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-3 methylphenyl) 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'-dihydroxydiphenylsulfide, 4 , 4'-dihydroxydiphenylsulfide, 6,6'-dihydroxy-3,3,3', 3'-tetramethylspirobiindane, preferably 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'-Tetramethylspirobiindan is more preferred.

For other details of the dihydroxy compound that brings about such a second structural unit, reference documents that disclose the dihydroxy compound relating to polycarbonate, for example, WO03 / 080728 Pamphlet, JP-A-6-172508, JP-A-8-27370, Japanese Patent Application Laid-Open No. 2001-55435, Japanese Patent Application Laid-Open No. 2002-117580, and the like can be referred to. The exemplified compound is an example of a dihydroxy compound that can be used as a constituent unit of a thermoplastic resin in the present invention, and is not limited thereto.

<Carbonate diester>
The polycarbonate in the present invention can obtain a dihydroxy compound that brings about the first structural unit and a dihydroxy compound that brings about the second structural unit by a transesterification reaction with a carbonic acid diester. The type of carbonic acid diester is not particularly limited as long as the polycarbonate according to 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 independently substituted or unsubstituted aromatic groups, respectively.)

The polycarbonate of the present invention has a terminal aromatic group derived from a carbonic acid diester represented by the above formula (2), particularly a terminal phenyl group, and the terminal aromatic group is measured by the method described in Examples. 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, still more preferably 100 μeq / g or less. Is.

When the concentration of the terminal aromatic group is within such a range, the hue immediately after polymerization or at the time of molding tends to be good, the hue after exposure to ultraviolet rays is also good, and the thermal 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 dihydroxy compound and the carbonic acid diester, which are the raw materials, the type and amount of the catalyst during the transesterification reaction, the pressure and temperature during the polymerization, etc. Can be mentioned.

<< Polycarbonate manufacturing method >>
According to the method for producing polycarbonate in the present invention, a dihydroxy compound that brings about a first structural unit, a dihydroxy compound that brings about a second structural unit, and a carbonic acid diester can be obtained in the presence of an alkali metal catalyst and / or an alkaline earth metal catalyst. Including transesterification reaction in. The above-mentioned polycarbonate of the present invention can be obtained by the method of the present invention. Therefore, for each configuration of the production method of the present invention, each configuration described with respect to the polycarbonate of the present invention can be referred to.

The polycarbonate in the present invention can be produced by a reaction means known per se for producing ordinary polycarbonate, for example, a method of reacting a dihydroxy component with a carbonic acid precursor such as a carbonic acid diester. Next, the basic means for 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 of distilling the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating in an inert gas atmosphere. .. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. Further, if necessary, a terminal terminator, an antioxidant or the like may be added.

Examples of the carbonic acid diester used in the transesterification reaction include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable. The amount of the diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, based on 1 mol of the total dihydroxy compound.

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

As such a compound, an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride, an alkoxide, a quaternary ammonium hydroxide, or the like of an alkali metal or an alkaline earth metal is preferably used, and these compounds are used. It can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, etc. Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples thereof include 2 lithium hydrogen acid, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium phenol salt, potassium salt, cesium salt, lithium salt and the like.

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

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having alkyl and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Can be mentioned. Examples thereof include bases or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

Other ester exchange catalysts include salts of zinc, tin, zirconium, lead, titanium, germanium, antimony and osmium, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), Tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxyde, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate ( IV) Titanium tetrabutoxide (IV) or the like is used. The catalysts used in International Publication No. 2011/010741 and JP-A-2017-179323 may be used.

Further, a catalyst composed of 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, and 1 × 10 ^-3 mol or more with respect to a total of 1 mol of all the monomer units used. It can be used in less than a mole, 8 × 10 ^-4 mol or less, and 6 × 10 ^{-4 mol or less.}

Examples of the aluminum salt include organic acid salts and inorganic acid salts of aluminum. Examples of the organic acid salt of aluminum include a carboxylate of aluminum, specifically, aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, and the like. Examples thereof include aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate. Examples of the inorganic acid salt of aluminum include aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, and aluminum phosphonate. Examples of the aluminum chelate compound include aluminum acetylacetonate, aluminum acetylacetone, aluminum ethylacetate acetate, and aluminum ethylacetate acetate diiso-propoxide.

Examples of the phosphorus compound include a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonic acid compound, a phosphinic acid compound, and a phosphine compound. 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 used is preferably 0.1 μmol to 500 μmol, more preferably 0.5 μmol to 300 μmol, and even more preferably 1 μmol to 100 μmol with respect to 1 mol of the dihydroxy component.

It is also possible to add a catalytic deactivator in the latter stage of the reaction. As the catalyst deactivating agent to be used, known catalyst deactivating agents are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acids are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as paratoluenesulfonic acid tetrabutylammonium salt are preferable.

As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluene sulfonate, phenyl paratoluene sulfonate and the like are preferably used. Of these, the tetrabutylphosphonium salt of dodecylbenzene sulfonic acid is most preferably used.

The amount of these catalyst deactivators used is preferably 0.5 to 50 mol per mole of the catalyst when at least one polymerization catalyst selected from the alkali metal compound and / or the alkaline earth metal compound is used. It can be used in proportions, more preferably 0.5 to 10 mol, and even more preferably 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 a linking group, and is produced, for example, from a dihydroxy compound represented by the above formula (1) and a dicarboxylic acid compound. In the present specification, the dicarboxylic acid compound means a compound having at least two carboxylic acid groups or carboxylic acid ester groups. Further, 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).

The dihydroxy compound that provides the first structural unit of the polyester carbonate in the present invention, the dihydroxy compound that provides the third structural unit, and the polycarbonate moiety are the dihydroxy compounds that provide the first structural unit described in Polycarbonate above. Reference can be made to the description of the portion of the dihydroxy compound and polycarbonate that results in the structural unit of 2.

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

For example, examples of the dicarboxylic acid compound that provides the second structural unit of the polyester carbonate in the present invention include malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, methylmalonic acid, ethylmalonic acid and the like. Alicyclic dicarboxylic acid compound such as aliphatic dicarboxylic acid compound, 2,6-decalindicarboxylic acid, monocyclic aromatic dicarboxylic acid compound such as heterocyclic dicarboxylic acid compound and phthalic acid, anthracendicarboxylic acid, phenanthrangecarboxylic acid. Examples of polycyclic aromatic dicarboxylic acid compounds such as 1,4-cyclohexanedicarboxylic acid, adamantandicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-bis ( Preferable examples thereof include carboxymethoxy) -1,1'binaphthyl, 9,9'-bis (2-carboxyethoxy) fluorene or an ester-forming derivative thereof (for example, dimethylterephthalate). These may be used alone or in combination of two or more types.

Examples of the carbonate precursor used for producing the polyester carbonate in the present invention include phosgene, diphenyl carbonate, bischlorohomete of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl. Examples thereof include carbonate and dinaphthyl carbonate, and among them, diphenyl carbonate is preferable.

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

In the reaction of a dihydroxy compound, a dicarboxylic acid or its acid chloride with phosgene, the reaction is carried out in a non-aqueous system in the presence of an acid binder and a solvent. As the acid binder, for example, pyridine, dimethylaminopyridine, tertiary amine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight modifier. 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 and a dicarboxylic acid or a diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is carried out under reduced pressure at usually 120 to 350 ° C., preferably 150 to 300 ° C. The degree of decompression is changed stepwise, and finally the alcohols produced at 133 Pa or less are distilled off from the system. The reaction time is usually about 1 to 4 hours. Further, in the transesterification reaction, a polymerization catalyst can be used to promote the 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 further use a nitrogen-containing basic compound as a secondary component, if necessary.

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

Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, and dimethylaminopyridine.

As the other transesterification catalyst, the catalyst listed as the transesterification catalyst can be similarly used in the above-mentioned method for producing polycarbonate.

After the polymerization reaction is completed, the polyester carbonate of the present invention may have the catalyst removed or deactivated in order to maintain thermal stability and hydrolysis 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-toluene sulfonic acid, and aromatic sulfonic acids such as butyl p-toluene sulfonic acid and hexyl p-toluene sulfonic acid. Esters, phosphoric acids such as sulphonic acid, sulphonic acid, phosphonic acid, triphenyl sulphonate, monophenyl sulphonate, diphenyl sulphonate, diethyl sulphonate, din-propyl sulphonate, sulphate Subphosphate esters such as din-butyl, din-hexyl sulfonate, dioctyl sulfonate, monooctyl sulfonate, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorus Phosphonates such as dioctyl acid and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid, phosphonic acid esters such as diethylphenylphosphonate, triphenylphosphine, bis (diphenylphosphino) ) Phosphins such as ethane, boric acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, organic halogens such as chloride stearate, benzoyl chloride and chloride p-toluenesulfonic acid. Compounds, 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, based on the amount of catalyst. If it is less than 0.01 times the molar amount of the catalyst amount, the deactivating effect becomes insufficient, which is not preferable. On the other hand, if the amount is more than 50 times the molar amount of the catalyst, the heat resistance is lowered and the molded product is easily colored, which is not preferable.

After the catalyst is deactivated, a step of volatilizing and removing the low boiling point compound 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 brings about these first structural units in the polyester of the present invention, the same thing as described for the above-mentioned polycarbonate can be said. Further, regarding the dicarboxylic acid compound that brings about the second structural unit, the same thing as described for the polyester carbonate described above can be said.

《Polyester manufacturing method》
When the thermoplastic resin of the present invention is 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 obtained reaction product is subjected to a polycondensation reaction to obtain a desired reaction product. It may be a high molecular weight compound.

As the polymerization method, an appropriate method can be selected 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) in which dicarboxylic acid chloride is dissolved in an organic solvent that is incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic dihydroxy compound and a polymerization catalyst, and the temperature is 50 ° C. Hereinafter, a method of carrying out the polymerization reaction while stirring at a temperature of preferably 25 ° C. or lower for 0.5 to 8 hours can be mentioned.

As the solvent used for the organic phase, a solvent that is incompatible with water and dissolves the polyester resin of the present invention is preferable. Examples of such a solvent include chlorine-based solvents such as methylene chloride, 1,2-dichloroethane, chloroform and chlorobenzene, and aromatic hydrocarbon-based solvents such as toluene, benzene and xylene, which are easy to use in production. Therefore, methylene chloride is preferable.

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

In the reaction by the melt polymerization method, it is usually preferable to mix a dihydroxy compound and a dicarboxylic acid compound or a diester thereof and react them at 120 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 270 ° C. The degree of decompression is changed stepwise, and finally, hydroxy compounds such as water and alcohol produced at 0.13 kPa or less are distilled off from the system, and the reaction time is usually about 1 to 10 hours.

Further, in the melting method, a transesterification catalyst and a polymerization catalyst can be used to increase the polymerization rate. As the ester exchange catalyst, a catalyst known per se can be adopted, and for example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium and lead elements can be used. Specific examples thereof include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Among these, compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, and alcoholates are preferable from the viewpoint of melt stability of the thermoplastic resin, hue, and a small amount of polymer insoluble foreign matter. Two or more of these compounds can be used in combination. As the polymerization catalyst, a catalyst known per se can be adopted, and for example, an antimony compound, a titanium compound, a germanium compound, a tin compound or an aluminum compound is preferable. Examples of such compounds include antimony, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like. In addition, these compounds can be used in combination of two or more. Among these, tin, titanium, and germanium compounds are preferable from the viewpoint of 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 with respect to 1 mol of the dicarboxylic acid compound, for example.

For the polyester resin of the present invention, an end sealant may be used for adjusting the molecular weight and improving the thermal stability. Examples of the terminal encapsulant include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, ketenimine compounds and the like.

<< Resin composition >>
Additives such as a mold release agent, a heat stabilizer, an ultraviolet absorber, a brewing agent, an antistatic agent, a flame retardant, a plasticizer, and a filler are appropriately added to the thermoplastic resin of the present invention, if necessary. Can be used as a resin composition. As a specific release agent and heat stabilizer, those described in Pamphlet 2011/010741 are preferably mentioned.

As a particularly preferable release agent, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used. 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 100% by weight. The release agent to be blended with 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 with respect to 100 parts by weight of the thermoplastic resin. The range of 0.02 to 0.5 parts by weight is preferable, and the range of 0.02 to 0.5 parts by weight is more preferable.

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

Particularly preferable phosphorus-based heat stabilizers include tris (2,4-di-tert-butylphenyl) phosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos. Fight, 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 preferable sulfur-based heat stabilizer is pentaerythritol-tetrakis (3-laurylthiopropionate). 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 phenolic heat stabilizers include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 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.

Phosphorus-based heat stabilizers and hindered phenol-based heat stabilizers can also be used in combination.

The UV absorber is at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. Is preferable.

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

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

Examples of triazine-based UV absorbers include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol and 2- (4,6-bis (4,6-bis). 2.4-Dimethylphenyl) -1,3,5-triazine-2-yl) -5-[(octyl) oxy] -phenol and the like can be mentioned.

As the cyclic iminoester-based ultraviolet absorber, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) is particularly preferable.

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

The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and within the range of such blending amount, a molded product of the thermoplastic resin depending on the application. It is possible to impart sufficient weather resistance to the resin.

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

When the optical lens is manufactured by injection molding, it is preferably molded 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 performed under the conditions of a cylinder temperature of 250 to 300 ° C. and a mold temperature of 80 to 170 ° C. When the cylinder temperature is higher than 350 ° C., the thermoplastic resin is decomposed and colored, and when the cylinder temperature is lower than 230 ° C., the melt viscosity is high and molding tends to be difficult. Further, 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 hardens too quickly in the mold at the time of molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Tends to be difficult.

As the optical lens of the present invention, it is preferably carried out in the form of an aspherical lens, if necessary. Since it is possible to eliminate spherical aberration with a single lens in an aspherical lens, it is not necessary to remove spherical aberration by combining a plurality of spherical lenses, resulting in weight reduction and reduction in molding cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

Further, since the thermoplastic resin of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens having a thin wall, a small size, and a complicated shape. 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, and further preferably 0.1 to 2.0 mm. The diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm. Further, it is preferable that the shape is a meniscus lens having a convex shape on one side and a concave shape on one side.

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

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

"Evaluation method"
(1) Sis isomer ratio (NMR)
The cis isomer ratio (molar ratio) of TMCBD was calculated by ¹ H NMR of JNM-ECZ400S / L1 manufactured by JEOL Ltd.
Sample 50 mg
Solvent Deuterated dimethyl sulfoxide 0.6 mL
Accumulation number: 512 times

(2) Amount of tertiary amine Triethylamine in TMCBD was quantified under the following equipment and conditions. A calibration curve was prepared using a triethylamine aqueous solution having a predetermined concentration for quantification.
Ion Chromatography Equipment: Dionex ICS-2000,
Column for cation measurement: Dionex IonPac CS17 (30 ° C)
Eluent: 5 mmol / L Methanesulfonic acid Flow rate: 1.0 mL / min Detector: Electrical conductivity (using autosuppressor)
Sample introduction amount: 100 μL

(3) Boric acid content Boric acid in TMCBD was quantified under the following equipment and conditions. A calibration curve was prepared using a boric acid aqueous solution having a predetermined concentration for quantification.
GC-MS analyzer: Agilent GC6890N, MSD5975B
Column: Agilent 19091S-433 HP-5MS
Measurement conditions: Flow rate 1 mL / min, column oven 50-310 ° C., measurement time 60 minutes Cyrilization method: Dissolve 10 mg of sample in acetonitrile, add 0.1 mL of pyridine and 0.1 mL of BSTFA (silylating agent), and filter. 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 heat was obtained from the signal intensity ratio based on the structural unit derived from each dihydroxy compound. The composition ratio of each structural unit in the plastic resin was calculated.
Thermoplastic resin amount 40 mg
Solvent deuterated chloroform 0.6 mL

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

^{(6) Terminal phenyl group concentration 1 1} H NMR was measured in the same manner as the above measurement of the thermoplastic resin composition ratio, and the terminal phenyl group concentration was determined by using 1,1,2,2-tetrabromoethane as an internal standard. It was determined from the signal intensity ratio based on the standard 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. _{The specific viscosity (η sp} ) of the solution at 20 ° C. was measured from a solution prepared by dissolving 0.7 g of a thermoplastic resin in 100 ml of methylene chloride. Then, Mv calculated by the following formula was used as 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: Extreme viscosity c: 0.7
Mv: Viscosity average molecular weight

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

(9) Initial Humor 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. Width 100 mm x width 100 mm x thickness 3 mm) was molded. The initial hue (YI ₀ ) of the molded plate was measured by SE-2000 (C light source, viewing angle 2 °) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7373.

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

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

(12) Refractive index (n _D ) and Abbe number 3 g of 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, the film was dried at 120 ° C. for 8 hours to prepare a film having a thickness of about 100 μm.

Using a DR-M2 Abbe refractometer manufactured by ATAGO, measure the refractive index (wavelength: 589 nm) and Abbe number (calculated from the refractive indexes at wavelengths: 486 nm, 589 nm, and 656 nm using the following formula) at 25 ° C. bottom.
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 wavelength 656 nm,
n _F : means the 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 was stretched twice at Tg + 10 ° C., and the phase difference (Re) at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The absolute value of birefringence was calculated.
| Δn | = | Re / d |
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)

(14) Optical distortion: The optical distortion was evaluated by sandwiching an aspherical lens formed by the method described in the production example between two polarizing plates and visually observing light leakage from behind by the orthogonal Nicol method. The evaluation was performed on the following three criteria.
・ Almost no light leakage ・ Slight light leakage is observed ・ Light leakage is remarkable

<< 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 Industries. 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 when the pH of the washing water reached 7 to 8 using ion-exchanged water at 40 ° C. Toluene was completely distilled off from the obtained toluene solution to obtain a white powder, which was then 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 ppm by weight, and a triethylamine content of 1350 ppm by weight. Subsequently, after dissolving in toluene, washing with 1% hydrochloric acid aqueous solution was carried out twice, and then washing with ion-exchanged water was carried out, and when the pH of the washing water reached 7 to 8, toluene was completely distilled off. The obtained 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 ppm by weight, and a triethylamine content of 350 ppm by weight.

<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 wt ppm, triethylamine content 350 wt ppm) 360 parts by weight, abbreviated as diphenyl carbonate (hereinafter DPC) 714 parts by weight, and tetramethylammonium hydroxide (hereinafter as catalyst, referred to as TMAH) 9.1 × ^{10 -2} parts by weight of lithium acetate 5.8 × ^10-2 parts by weight was heated to 180 ° C. in a nitrogen atmosphere to melt it.

Then, the temperature was raised to 240 ° C. over 2 hours, and the pressure in the reactor was reduced from 101.3 kPa to 13.4 kPa over 40 minutes while distilling off the by-produced phenol. Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.4 kPa and further distilling off phenol. The internal pressure was reduced from 13.4 kPa to 2 kPa in absolute pressure, and the temperature was further raised to 260 ° C. to remove distilling phenol from the system. After that, the degree of decompression was set to 133 Pa or less over 1 hour. The polycondensation reaction was terminated when a predetermined stirring power was obtained. Pellets were obtained by discharging from the bottom of the reaction tank under nitrogen pressurization and cutting with a pelletizer while cooling in a water tank. Various evaluations were performed on the pellets, and the evaluation results are shown in Table 1.

Based on the weight of the resin, 0.05% by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.10% by weight of glycerin monostearate were added, and a φ15 mm twin-screw extruder with a vent was used. And pelletized. The pellet was dried at 120 ° C. for 4 hours and then 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. When the obtained aspherical lens was sandwiched between two polarizing plates and the optical distortion was evaluated by visually observing the light leakage from the back by the orthogonal Nicol method, a slight light leakage was observed.

<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 TMC259 parts by weight and TMCBD360 parts by weight, 308 parts by weight of 6,6'-dihydroxy-3,3,3', 3'-tetramethyl-1,1'-spirobiindan (hereinafter abbreviated as SBI) and 336 parts by weight of TMCBD Polycarbonate was obtained in the same manner as in Example 1 except that the above was used. When the optical strain 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 above. When the optical strain 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. And obtained polycarbonate. When the optical strain was evaluated by the same method as in Example 1, a slight amount of 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>
TMC155 parts, TMCBD360 parts, DPC673 parts, (abbreviated as DMT) dimethyl terephthalate and except for using titanium tetrabutoxide 11.3 × ^{10 -2} parts by weight as a catalyst, in the same manner as in Example 1, a polyester I got carbonate. When the optical strain was evaluated by the same method as in Example 1, a slight amount of 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 amount was changed with the dihydroxy compound.

<Example 17>
Polycarbonate was obtained in the same manner as in Example 1 except that the amounts were changed from TMC83 parts by weight and TMCBD350 parts by weight, and BPAF213 parts by weight was used instead of TMC259 parts by weight and TMCBD360 parts by weight. When the optical strain was evaluated by the same method as in Example 1, a slight amount of light leakage was observed.

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

The results for polyester carbonate are summarized in Table 2 below.

Data on the refractive index and the like of various polymers are summarized in Table 3 below.

The refractive indexes and Abbe numbers of the various polymers shown in Examples 1 to 17 and Table 3 are plotted in FIG.

As shown by the "limit line of the prior art" in FIG. 1, in various prior art homopolymers other than the TMCBD homopolymer, the refractive index (n _D ) and the Abbe number (ν) are calculated by the following mathematical formulas (ν). 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 the monomers constituting these polycarbonates are copolymerized at a weight ratio of 1: 1, the refractive index and Abbe number are approximately intermediate between the refractive index and Abbe number of these homopolymers. Has been done. Therefore, in the resin of the prior art, the refractive index (n _D ) and the Abbe number (ν) satisfy the relationship of the above mathematical formula (B) shown by the “limit 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 mathematical formula (B) but satisfies the following mathematical 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 birefringence, heat resistance and moldability as resins for lenses. Further, since the thermoplastic resins of Examples 1 to 17 do not substantially contain heterocyclic amines, it can be said that they are excellent in hue from this point as well.

Claims (16)

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

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and 3 to 10 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 6 to 10 carbon atoms aryl groups, 7 to 20 carbon atoms aralkyl groups, 6 to 10 carbon atoms aryloxy groups or carbon atoms It shows the aralkyloxy group of the number 7 to 20 or a halogen atom; the cyclobutane ring indicates either a cis-trans isomer mixture, a cis isomer alone, or a trans isomer alone);
It has a second structural unit derived from a dihydroxy compound or a dicarboxylic acid compound, and has a refractive index (n _D ) and an Abbe number (ν) that satisfy the following mathematical formula (A).
Thermoplastic resin for lenses:
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 carbonic acid diester represented by the following formula (2):

(In the formula, R ₅ and R ₆ are independently substituted or unsubstituted aromatic groups, respectively). The second structural unit is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, a heterocyclic dihydroxy compound and an aromatic dihydroxy compound, and an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and a heterocyclic dicarboxylic acid compound. The thermoplastic resin according to claim 1 or 2, which is obtained from at least one compound selected from the group consisting of an aromatic dicarboxylic acid compound. The thermoplastic resin according to any one of claims 1 to 3, wherein the first structural unit is contained in an amount of more than 50 mol% and 95 mol% or less. The thermoplastic resin according to any one of claims 1 to 4, wherein the refractive index (n _{D) is more than 1.470 and 1.600 or less.} The thermoplastic resin according to any one of claims 1 to 5, wherein the Abbe number (ν) is in the range of 25 or more and 50 or less. The thermoplastic resin according to any one of claims 1 to 6, which has a _{refractive index (n D} ) and an Abbe number (ν) satisfying 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 7, wherein the glass transition temperature is in the range of 130 ° C. to 170 ° C. The heat according to any one of claims 1 to 8, wherein _{the initial hue (YI 0} ) measured in accordance with JIS K7373 for a molded plate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm is 4.0 or less. Plastic resin. The thermoplastic resin according to any one of claims 1 to 9, which is substantially free of heterocyclic amines. The thermoplastic resin according to any one of claims 1 to 10, which is polycarbonate or polyester carbonate. Transesterification of the dihydroxy compound that brings about the first structural unit, the dihydroxy compound that brings about the second structural unit, and the carbonate diester in the presence of an alkali metal catalyst and / or an alkaline earth metal catalyst. The method for producing a thermoplastic resin according to any one of claims 1 to 11, which is characteristic. The dihydroxy compound that yields the first structural unit, the dicarboxylic acid compound that yields the second structural unit, and the carbonic acid diester are esterified in the presence of a titanium compound catalyst or in the presence of an aluminum and phosphorus compound catalyst. / Or The method for producing a thermoplastic resin according to any one of claims 1 to 11, wherein the ester exchange reaction is carried out. The method for producing a thermoplastic resin according to claim 12 or 13, wherein the tertiary amine content of the dihydroxy compound that provides the first structural unit is 1000 ppm by weight or less. The method for producing a thermoplastic resin according to any one of claims 12 to 14, wherein the boric acid content of the dihydroxy compound that brings about the first structural unit is 100 ppm by weight or less. An optical lens comprising the thermoplastic resin according to any one of claims 1 to 11.

Images