JP7559361B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a polycarbonate resin-based thermoplastic resin composition that not only can adjust the refractive index of the polycarbonate resin even with a smaller alloy ratio while maintaining the transparency of the polycarbonate resin, but also has high heat resistance, and to an injection molded article, sheet, and film made using the thermoplastic resin composition.

Polycarbonate resin (hereinafter sometimes referred to as "PC") has been used in fields such as exteriors, electronic and electrical applications, and optical disk substrates due to its characteristics such as heat resistance, impact resistance, and transparency. Furthermore, as its applications in automobiles and medical materials expand, there is an increasing demand for thermoplastic resin compositions that not only maintain the transparency of PC, but also adjust the refractive index of PC with a smaller alloy ratio, and have high heat resistance.

The refractive index of PC is about 1.58 to 1.59, and it is possible to use polyethylene terephthalate (hereinafter sometimes referred to as "PET") as a modifier for PC to adjust the refractive index, but it is known that adding PET significantly impairs the transparency of PC. As a countermeasure to this, methods of extending the residence time during melt mixing and methods of using a Ti-based catalyst as a catalyst during melt mixing have been considered. However, this method does not provide sufficient transparency, and furthermore, there are problems such as yellowing of the composition due to thermal decomposition and generation of gases such as aldehydes due to decomposition. Furthermore, there is a problem that the heat resistance of the resin composition is significantly reduced because the glass transition temperature (Tg) of PET is relatively low.

When polybutylene terephthalate resin (hereinafter sometimes referred to as "PBT") is used as a modifier for PC, the transparency is relatively good, but it is not sufficient, and there is also a problem that the heat resistance is significantly reduced. In addition, a thermoplastic resin composition of modified PET in which 40 mol % of the diol constituent units are 1,4-cyclohexanedimethanol units and PC has been proposed (see Patent Document 1), but although this resin composition has good transparency, there is a problem that the heat resistance is reduced.

Technologies have been proposed for thermoplastic resin compositions with excellent transparency consisting of polycarbonate resin and a specific copolymerized polyester resin, as well as injection molded articles, sheets, and films made using said thermoplastic resin compositions (see Patent Document 2), but the heat resistance is insufficient, and because the refractive index of said copolymerized polyester resin is large, it is necessary to melt-mix a larger amount of copolymerized polyester resin to adjust the refractive index of the base resin, PC, and in this case, it is not possible to maintain the transparency of PC. Therefore, no polyester resin-added polycarbonate resin-based thermoplastic resin composition is known that not only can adjust the refractive index of PC with a smaller alloy ratio while maintaining the transparency of PC, but also has high heat resistance.

In addition, polyester resin (hereinafter sometimes referred to as "PE"), polycarbonate resin, polyester carbonate resin (hereinafter sometimes referred to as "PEC"), etc. are known as thermoplastic resins (Patent Documents 3 to 7). However, no polycarbonate resin-based thermoplastic resin composition is known that uses these thermoplastic resins as a modifier for PC, and that not only can adjust the refractive index of PC even with a smaller alloy ratio while maintaining the transparency of PC, but also has high heat resistance.

JP 2000-63641 A JP 2003-246925 A Patent No. 4062416 Patent No. 5445652 JP 2014-044394 A Special table 2016-525610 publication Special table 2018-504497 publication

In view of the above circumstances, the present invention provides a PC-based thermoplastic resin composition that not only maintains the transparency of PC while adjusting the refractive index of PC even with a smaller alloy ratio, but also has high heat resistance, as well as injection molded articles, sheets, and films made from the thermoplastic resin composition.

As a result of extensive investigations to solve the above problems, the inventors discovered that a thermoplastic resin composition obtained by blending a polycarbonate resin with a polycondensate containing a certain proportion of a diol having a specific cyclic acetal skeleton as a diol structural unit not only maintains the transparency of PC while adjusting the refractive index of PC even with a smaller alloy ratio, but also has high heat resistance, leading to the completion of the present invention.

That is, the present invention includes the following aspects <1> to <21>.

＜1＞
A thermoplastic resin composition (C) comprising a polycarbonate resin (A) and a polycondensate (B),
The thermoplastic resin composition (C) contains 40 to 99% by weight of a polycarbonate resin (A) and 60 to 1% by weight of a polycondensate (B), and the polycondensate (B) is selected from at least one resin selected from the group consisting of a polyester resin (B1), a polycarbonate resin (B2), and a polyester carbonate resin (B3);
The polyester resin (B1) contains, in its diol constituent units,
(i) 61 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) containing 0 to 39 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton and/or an alicyclic diol (b2);
The polycarbonate resin (B2) contains, in its diol constituent units,
(i) 1 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) containing 0 to 99 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton and/or an alicyclic diol (b2);
The polyester carbonate resin (B3) contains, in its diol constituent units,
(i) containing 1 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton;
Thermoplastic resin composition (C).

（式中、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、炭素数１～１０の非環状炭化水素基、炭素数５～１０の脂環式炭化水素基から選ばれ；
Ｒ_３及びＲ_４は、それぞれ独立して、水素原子、炭素数１～１０の非環状炭化水素基、ハロゲン原子、置換または非置換のフェニル基から選ばれ；
ｍ及びｎはそれぞれ独立して１または２であり；
ｋは４または５である。） ＜2＞
The thermoplastic resin composition (C) according to the above item <1>, wherein the polycarbonate resin (A) is a polycarbonate resin composed of repeating units represented by general formula (1) and/or (2).

(Wherein,
R ₁ and R ₂ are each independently selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, and an alicyclic hydrocarbon group having 5 to 10 carbon atoms;
R ₃ and R ₄ are each independently selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a substituted or unsubstituted phenyl group;
m and n are each independently 1 or 2;
k is 4 or 5.

＜3＞
The thermoplastic resin composition (C) according to the above item <1>, wherein the polycarbonate resin (A) is a polycarbonate ester of bisphenol.

＜4＞
The thermoplastic resin composition (C) according to the above item <3>, wherein the bisphenol is selected from the group consisting of bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD and bisphenol MIBK.

（式中、Ｒ_５及びＲ_６はそれぞれ独立して、炭素数が１～１０の非環状炭化水素基、炭素数が３～１０の脂環式炭化水素基、及び炭素数が６～１０の芳香族炭化水素基から選ばれる特性基を表す。） ＜5＞
The thermoplastic resin composition (C) according to any one of the above items <1> to <4>, wherein the diol component (a1) having a spiro ring-containing cyclic acetal skeleton is represented by general formula (3):

(In the formula, _R5 and _R6 each independently represent a characteristic group selected from a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.)

（式中、
Ｒ_５は前記と同様であり；
Ｒ_７は炭素数が１～１０の非環状炭化水素基、炭素数が３～１０の脂環式炭化水素基、及び炭素数が６～１０の芳香族炭化水素基から選ばれる特性基を表す。） ＜6＞
The thermoplastic resin composition (C) according to any one of the above items <1> to <5>, wherein the diol component (b1) having a non-spiro ring-containing cyclic acetal skeleton is represented by general formula (4):

(Wherein,
R ₅ is as defined above;
_R7 represents a characteristic group selected from a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.

（式中、
Ｒ_８、Ｒ_９、Ｒ_１０及びＲ_１１はそれぞれ独立して、水素原子、炭素数１～６の非環状炭化水素基から選ばれ；
ｐ、ｑ、ｒ及びｓはそれぞれ独立して、０、１または２である。） ＜７＞
The thermoplastic resin composition (C) according to any one of the above <1> to <6>, wherein the alicyclic diol (b2) is represented by general formula (5):

(Wherein,
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 6 carbon atoms;
p, q, r and s are each independently 0, 1 or 2.

＜8＞
The thermoplastic resin composition (C) according to any one of the above <1> to <7>, wherein the dicarboxylic acid constituent unit of the polyester carbonate (B3) contains an alicyclic dicarboxylic acid or a diester thereof (b3).

（式中、
Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、およびＲ_１３それぞれ独立して、水素原子、炭素数１～６の非環状炭化水素基から選ばれ；
ｐ及びｑはそれぞれ独立して、０、１または２である。） ＜9＞
The thermoplastic resin composition (C) according to any one of the above <1> to <8>, wherein the alicyclic dicarboxylic acid or its diester (b3) is represented by general formula (6):

(Wherein,
R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each independently selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 6 carbon atoms;
p and q are each independently 0, 1 or 2.

＜10＞
The thermoplastic resin composition (C) according to any one of the above items <1> to <9>, wherein the diol component (a1) having a spiro ring-containing cyclic acetal skeleton is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

<11>
The thermoplastic resin composition (C) according to any one of the above items <1> to <10>, wherein the diol component (b1) having a spiro ring-free cyclic acetal skeleton is 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane.

＜12＞
The thermoplastic resin composition (C) according to any one of the above <1> to <11>, wherein the alicyclic diol (b2) is 1,4-cyclohexanedimethanol.

＜13＞
The thermoplastic resin composition (C) according to the above-mentioned <8>, wherein the alicyclic dicarboxylic acid or its diester (b3) is 1,4-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylate dimethyl.

＜14＞
The polyester resin (B1) contains, in its diol constituent units,
Diol (a1) having a spiro ring-containing cyclic acetal skeleton, and Diol (b1) having a non-spiro ring-containing cyclic acetal skeleton.
The thermoplastic resin composition (C) according to any one of <1> to <13> above,

＜15＞
The polyester resin (B1) contains, in its diol constituent units,
Diol (a1) having a spiro ring-containing cyclic acetal skeleton;
A diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and an alicyclic diol (b2).
The thermoplastic resin composition (C) according to any one of <1> to <13> above,

＜16＞
The thermoplastic resin composition (C) according to any one of <1> to <15>, wherein the dicarboxylic acid constituent unit of the polyester resin (B1) is a dicarboxylic acid unit selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue.

＜１７＞
The thermoplastic resin composition (C) according to any one of the above <1> to <16>, which has the following physical properties (i) to (iii):
(i) A glass transition temperature measured by a differential scanning calorimeter is 130°C or higher. (ii) A total light transmittance of a 1 mm thick injection molded article is 87% or higher and a haze value is 4% or less. (iii) A refractive index measured by the critical angle method is 1.45 to 1.60.

＜18＞
A sheet obtained by using the thermoplastic resin composition (C) according to any one of <1> to <17> above, the sheet having a total light transmittance of 87% or more when it is 500 μm thick.

＜19＞
A film obtained by using the thermoplastic resin composition (C) according to any one of the above items <1> to <17>, the film having a haze of 4% or less when it has a thickness of 50 μm.

＜20＞
A blend composition (E) of the thermoplastic resin composition (C) according to any one of the above items <1> to <17> and the thermoplastic resin composition (D), wherein a difference in refractive index between the thermoplastic resin composition (C) and the thermoplastic resin composition (D) measured by a critical angle method is 0.02 or less.

＜21＞
The blend composition (E) according to the above-mentioned <20>, wherein the thermoplastic resin composition (D) is a thermoplastic resin composition containing at least one thermoplastic resin selected from a polyetherester resin, a polyamide resin, an acrylic resin, a polyvinyl chloride resin, and a polycarbonate resin.

The present invention not only makes it possible to adjust the refractive index of polycarbonate resin even with a smaller alloy ratio while maintaining the transparency of the polycarbonate resin, but also makes it possible to obtain a polycarbonate resin-thermoplastic resin composition with high heat resistance.

1. Thermoplastic resin composition (C)
The thermoplastic resin composition (C) of the present invention contains a polycarbonate resin (A) and a polycondensate (B).

In one embodiment of the present invention, the thermoplastic resin composition (C) may comprise 40 to 99% by weight of polycarbonate resin (A) and 60 to 1% by weight of polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may comprise 40 to 95% by weight of polycarbonate resin (A) and 60 to 5% by weight of polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may comprise 50 to 99% by weight of polycarbonate resin (A) and 50 to 1% by weight of polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may comprise 50 to 95% by weight of polycarbonate resin (A) and 50 to 5% by weight of polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may comprise 60 to 99% by weight of polycarbonate resin (A) and 40 to 1% by weight of polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 60 to 95% by weight of the polycarbonate resin (A) and 40 to 5% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 70 to 99% by weight of the polycarbonate resin (A) and 30 to 1% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 70 to 95% by weight of the polycarbonate resin (A) and 30 to 5% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 75 to 99% by weight of the polycarbonate resin (A) and 25 to 1% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 75 to 95% by weight of the polycarbonate resin (A) and 25 to 5% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 80 to 99% by weight of the polycarbonate resin (A) and 20 to 1% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 80 to 95% by weight of the polycarbonate resin (A) and 20 to 5% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 90 to 99% by weight of the polycarbonate resin (A) and 10 to 1% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 90 to 95% by weight of the polycarbonate resin (A) and 10 to 5% by weight of the polycondensate (B). In one embodiment of the present invention, the thermoplastic resin composition (C) may contain 95 to 99% by weight of the polycarbonate resin (A) and 5 to 1% by weight of the polycondensate (B).

In the thermoplastic resin composition (C) of the present invention, by adjusting the compounding ratio of the polycarbonate resin (A) and the polycondensate (B) within the above range, not only can the refractive index of the polycarbonate resin be adjusted, but also a polycarbonate resin-thermoplastic resin composition having high heat resistance can be obtained. In addition, by being able to appropriately adjust the refractive index, transparency can be ensured even when a blend composition with other resin compositions is produced.

The thermoplastic resin composition (C) of the present invention can be obtained by kneading the polycarbonate resin (A) and the polycondensate (B) by a conventional method.

（式中、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、炭素数１～１０の非環状炭化水素基、炭素数５～１０の脂環式炭化水素基から選ばれ；
Ｒ_３及びＲ_４は、それぞれ独立して、水素原子、炭素数１～１０の非環状炭化水素基、ハロゲン原子、置換または非置換のフェニル基から選ばれ；
ｍ及びｎはそれぞれ独立して１または２であり；
ｋは４または５である。） 2. Polycarbonate resin (A)
In the present invention, the polycarbonate resin (A) may be composed of repeating units represented by general formula (1) and/or (2).

(Wherein,
R ₁ and R ₂ are each independently selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, and an alicyclic hydrocarbon group having 5 to 10 carbon atoms;
R ₃ and R ₄ are each independently selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a substituted or unsubstituted phenyl group;
m and n are each independently 1 or 2;
k is 4 or 5.

In one embodiment of the present invention, in the above general formula (1), R ₁ and R ₂ are each independently selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 4 carbon atoms, and an alicyclic hydrocarbon group having 5 to 7 carbon atoms.

In one embodiment of the present invention, in the above general formula (1), R ₁ and R ₂ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, but are not limited thereto. In a preferred embodiment, R ₁ and R ₂ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, or cycloheptyl.

In one embodiment of the present invention, in the above general formulas (1) and (2), _R3 and _R4 are each independently selected from a hydrogen atom, an acyclic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, and a substituted or unsubstituted phenyl group.

In one embodiment of the present invention, in the above general formulas (1) and (2), R ₃ and R ₄ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, chloro, fluoro, bromo, iodo, or phenyl, but are not limited thereto. In a preferred embodiment, R ₃ and R ₄ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or isobutyl.

In the present invention, the polycarbonate resin (A) may be a polycarbonate ester of bisphenol.

In one embodiment of the present invention, the bisphenol may be selected from the group consisting of, for example, but not limited to, bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD and bisphenol MIBK.

In one embodiment of the present invention, the polycarbonate resin (A) may be a polycarbonate ester of bisphenol A.

The polycarbonate resin (A) used in the present invention can be produced by conventional methods.

3. Polycondensate (B)
In the present invention, the polycondensate (B) is selected from at least one resin selected from the following polyester resin (B1), polycarbonate resin (B2), and polyester carbonate resin (B3). The polycondensate (B) can be produced by any of the conventional methods.

(1) Polyester resin (B1)
In the present invention, the polyester resin (B1) contains, in its diol constituent units,
(i) a diol (a1) having a spiro ring-containing cyclic acetal skeleton;
(ii) A diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2). The polyester resin (B1) may further contain a diol other than the above in its diol constituent units.

In one embodiment of the present invention, the polyester resin (B1) may contain, in its diol constituent units, (i) a diol (a1) having a spiro ring-containing cyclic acetal skeleton in an amount of more than 60 mol%, for example, 61 mol%, 62 mol%, 63 mol%, 64 mol%, 65 mol%, 66 mol%, 67 mol%, 68 mol%, 69 mol%, 70 mol%, 71 mol%, 72 mol%, 73 mol%, 74 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 99 mol%, or 100 mol%.

In one embodiment of the present invention, the polyester resin (B1) may contain, in its diol constituent units, (ii) a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2) in an amount of less than 40 mol%, for example, 39 mol%, 38 mol%, 37 mol%, 36 mol%, 35 mol%, 34 mol%, 33 mol%, 32 mol%, 31 mol%, 30 mol%, 29 mol%, 28 mol%, 27 mol%, 26 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 1 mol%, or 0 mol%.

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
(i) 61 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) The copolymer may contain 0 to 39 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2).

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
(i) 65 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) It may contain 0 to 35 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2).

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
(i) 70 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) It may contain 0 to 30 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2).

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
(i) 75 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) It may contain 0 to 25 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2).

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
Diol (a1) having a spiro ring-containing cyclic acetal skeleton, and Diol (b1) having a non-spiro ring-containing cyclic acetal skeleton.
Includes.

In one embodiment of the present invention, the polyester resin (B1) has, in its diol constituent unit,
Diol (a1) having a spiro ring-containing cyclic acetal skeleton;
A diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and an alicyclic diol (b2).
Includes.

In one embodiment of the present invention, the dicarboxylic acid constituent unit of the polyester resin (B1) may be a dicarboxylic acid unit selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue. In a preferred embodiment of the present invention, the dicarboxylic acid constituent unit of the polyester resin (B1) may be a terephthalic acid residue or a 1,4-cyclohexanedicarboxylic acid residue.

(2) Polycarbonate resin (B2)
In the present invention, the polycarbonate resin (B2) contains, in its diol constituent units,
(i) a diol (a1) having a spiro ring-containing cyclic acetal skeleton;
(ii) A diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2). The polyester resin (B2) may further contain a diol other than the above in its diol constituent units.

In one embodiment of the present invention, the polycarbonate resin (B2) may contain, in its diol constituent units, (i) a diol (a1) having a spiro ring-containing cyclic acetal skeleton in an amount greater than 0 mol%, for example, 1 mol%, 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, 99 mol%, or 100 mol%.

In one embodiment of the present invention, the polycarbonate (B2) may contain, in its diol constituent units, (ii) a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton, and/or an alicyclic diol (b2) in an amount of less than 100 mol%, for example, 99 mol%, 98 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2 mol%, 1 mol%, or 0 mol%.

In one embodiment of the present invention, the polycarbonate resin (B2) contains, in its diol constitutional unit,
(i) 1 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) The diol (b1) having a non-spiro ring-containing cyclic acetal skeleton and/or the alicyclic diol (b2) may be contained in an amount of 0 to 99 mol %.

(3) Polyester carbonate resin (B3)
In one embodiment of the present invention, the polyester carbonate resin (B3) contains, as its diol constituent unit,
(i) Diol having a spiro ring-containing cyclic acetal skeleton (a1)
may include.

In one embodiment of the present invention, the polyester carbonate resin (B3) may contain, in its diol constituent units, (i) a diol (a1) having a spiro ring-containing cyclic acetal skeleton in an amount greater than 0 mol%, for example, 1 mol%, 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 98 mol%, 99 mol%, or 100 mol%.

In one embodiment of the present invention, the polyester carbonate resin (B3) has, in its diol constituent unit,
(i) The diol (a1) having a spiro ring-containing cyclic acetal skeleton may be contained in an amount of 1 to 100 mol %.

In one embodiment of the present invention, the polyester carbonate resin (B3) may contain an alicyclic dicarboxylic acid or its diester (b3) as its dicarboxylic acid constituent unit. The polyester resin (B3) may additionally contain a diol other than the above in its diol constituent unit.

（式中、Ｒ_５及びＲ_６はそれぞれ独立して、炭素数が１～１０の非環状炭化水素基、炭素数が３～１０の脂環式炭化水素基、及び炭素数が６～１０の芳香族炭化水素基から選ばれる特性基を表す。） (4) Diol having a spiro ring-containing cyclic acetal skeleton (a1)
In the present invention, the diol component (a1) having a spiro ring-containing cyclic acetal skeleton can be represented by general formula (3).

(In the formula, _R5 and _R6 each independently represent a characteristic group selected from a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.)

In one embodiment of the present invention, in the above general formula (3), _R5 and _R6 can be independently selected from a non-cyclic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, and a phenylene group.

In one embodiment of the present invention, in the above general formula (3), _R5 and _R6 may each independently be a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as, but not limited to, a dimethylethylenyl group, an isopropylene group, an isobutylene group, or a phenylene group. In a preferred embodiment, _R5 and _R6 may each independently be a methylene group, an ethylene group, a propylene group, a butylene group, or a dimethylethylenyl group.

In one embodiment of the present invention, the diol component (a1) having a spiro ring-containing cyclic acetal skeleton is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

（式中、
Ｒ_５は前記と同様であり；
Ｒ_７は炭素数が１～１０の非環状炭化水素基、炭素数が３～１０の脂環式炭化水素基、及び炭素数が６～１０の芳香族炭化水素基から選ばれる特性基を表す。） (5) Diol having a non-spiro ring-containing cyclic acetal skeleton (b1)
In the present invention, the diol component (b1) having a non-spiro ring-containing cyclic acetal skeleton can be represented by general formula (4).

(Wherein,
R ₅ is as defined above;
_R7 represents a characteristic group selected from a non-cyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.

In one embodiment of the present invention, in the above general formula (4), R ₅ can be selected from a non-cyclic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, and a phenylene group.

In one embodiment of the present invention, in the above general formula (4), _R5 may be, but is not limited to, a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof, such as a dimethylethylenyl group, an isopropylene group, an isobutylene group, or a phenylene group. In a preferred embodiment, _R5 may be a methylene group, an ethylene group, a propylene group, a butylene group, or a dimethylethylenyl group.

In one embodiment of the present invention, in the above general formula (4), R ₇ can be selected from a hydrogen atom, a non-cyclic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, and a substituted or unsubstituted phenyl group.

In one embodiment of the present invention, in the above general formula (4), R ₇ may be, but is not limited to, a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, o-methylphenyl, m-methylphenyl, or p-methylphenyl. In a preferred embodiment, R ₇ may be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, or phenyl.

In one embodiment of the present invention, the diol component (b1) having a non-spiro ring-containing cyclic acetal skeleton is 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane.

（式中、
Ｒ_８、Ｒ_９、Ｒ_１０及びＲ_１１はそれぞれ独立して、水素原子、炭素数１～６の非環状炭化水素基から選ばれ；
ｐ、ｑ、ｒ及びｓはそれぞれ独立して、０、１または２である。） (6) Alicyclic diol (b2)
In the present invention, the alicyclic diol (b2) can be represented by general formula (5).

(Wherein,
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 6 carbon atoms;
p, q, r and s are each independently 0, 1 or 2.

In one embodiment of the present invention, in the above general formula (5), R ₈ , R ₉ , R ₁₀ and R ₁₁ can be selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 4 carbon atoms.

In one embodiment of the present invention, in the above general formula (5), R ₈ , R ₉ , R ₁₀ and R ₁₁ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, but are not limited thereto. In a preferred embodiment, R ₈ , R ₉ , R ₁₀ and R ₁₁ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl.

In one embodiment of the present invention, the alicyclic diol (b2) may be, but is not limited to, 1,4-cyclohexanedimethanol, 1,3-cyclopentanedimethanol, 1,3-cyclobutanedimethanol, 1,3-cyclobutanediol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

In one embodiment of the present invention, the alicyclic diol (b2) is 1,4-cyclohexanedimethanol.

（式中、
Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、およびＲ_１３それぞれ独立して、水素原子、炭素数１～６の非環状炭化水素基から選ばれ；
ｐ及びｑはそれぞれ独立して、０、１または２である。） (7) Alicyclic dicarboxylic acid or diester thereof (b3)
In the present invention, the alicyclic dicarboxylic acid or diester thereof (b3) is represented by the general formula (6).

(Wherein,
R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each independently selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 6 carbon atoms;
p and q are each independently 0, 1 or 2.

In one embodiment of the present invention, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the above general formula (6) can be selected from a hydrogen atom and a non-cyclic hydrocarbon group having 1 to 4 carbon atoms.

In one embodiment of the present invention, in the above general formula (6), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, but are not limited thereto. In a preferred embodiment, R ₈ , R ₉ , R ₁₀ and R ₁₁ may each independently be a hydrogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl.

In one embodiment of the present invention, the alicyclic dicarboxylic acid or its diester (b3) may be, but is not limited to, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylate, or diethyl 1,4-cyclohexanedicarboxylate.

In one embodiment of the present invention, the alicyclic dicarboxylic acid or its diester (b3) is 1,4-cyclohexanedicarboxylic acid or dimethyl 1,4-cyclohexanedicarboxylate.

4. Physical properties of thermoplastic resin composition (C) The thermoplastic resin composition (C) of the present invention can adjust the refractive index of the polycarbonate resin even with a smaller alloy ratio while maintaining the transparency of the polycarbonate resin, and can also have high heat resistance. The thermoplastic resin composition (C) of the present invention was evaluated according to the following items.

(1) Glass transition temperature (Tg)
The thermoplastic resin composition (C) of the present invention may have a glass transition temperature of 90° C. or more and 160° C. or less. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a glass transition temperature of, for example, 90° C. or more, 95° C. or more, 100° C. or more, 105° C. or more, 110° C. or more, 115° C. or more, 120° C. or more, 125° C. or more, 130° C. or more, 135° C. or more, 140° C. or more, 145° C. or more, 150° C. or more, but is not limited to these. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a glass transition temperature of, for example, 110° C. or more and less than 130° C., 130° C. or more and less than 140° C., 140° C. or more and less than 149° C., 149° C. or more and 160° C. or less, but is not limited to these ranges.

The glass transition temperature can be measured by conventional methods. For example, the glass transition temperature can be measured using a differential scanning calorimeter.

(2) Total Light Transmittance The thermoplastic resin composition (C) of the present invention may have a total light transmittance of 87% or more when injected into a 1 mm-thick injection molded article. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a total light transmittance of, for example, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, etc. when injected into a 1 mm-thick injection molded article.

The total light transmittance can be measured by a conventional method. For example, the total light transmittance can be measured in accordance with JIS K7105 using a color and turbidity simultaneous measuring instrument (model: COH-400) manufactured by Nippon Denshoku Industries Co., Ltd.

(3) Haze The thermoplastic resin composition (C) of the present invention may have a haze of 4% or less when injected into a 1 mm-thick article. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a total light transmittance of 4.0%, 3.5%, 3.0%, 2.5%, 2.0%, 1.5%, 1.0%, 0.5%, 0.3%, 0.1%, 0%, etc. when injected into a 1 mm-thick article.

Haze value can be measured by a conventional method. For example, the haze value can be measured according to JIS K7105 using a simultaneous color and turbidity meter (model: COH-400) manufactured by Nippon Denshoku Industries Co., Ltd.

(4) Refractive Index The thermoplastic resin composition (C) of the present invention may have a refractive index measured by the critical angle method of 1.45 to 1.60. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a refractive index measured by the critical angle method of, for example, 1.45 to 1.60, 1.45 to 1.58, 1.45 to 1.57, 1.45 to 1.56, 1.45 to 1.55, 1.45 to 1.54, 1.45 to 1.50, 1.50 to 1.60, 1.50 to 1.58, 1.50 to 1.57, 1.50 to 1.56, 1.50 to 1.55, 1.50 to 1.54, 1. 54 to 1.60, 1.54 to 1.58, 1.54 to 1.57, 1.54 to 1.56, 1.54 to 1.55, 1.55 to 1.60, 1.55 to 1.58, 1.55 to 1.57, 1.55 to 1.56, 1.56 to 1.60, 1.56 to 1.58, 1.56 to 1.57, 1.57 to 1.60, 1.57 to 1.58, 1.58 to 1.60, 1.59 to 1.60, etc., but are not limited thereto. In one embodiment of the present invention, the thermoplastic resin composition (C) may have a refractive index measured by a critical angle method of, for example, 1.50 or more and less than 1.54, 1.54 or more and less than 1.56, 1.56 or more and less than 1.57, 1.57 or more and less than 1.58, etc., but are not limited thereto.

In the present invention, the refractive index can be measured by the critical angle method using an injection molded body with a thickness of 1.0 mm in accordance with JIS K7142 using a multi-wavelength Abbe refractometer (model: DR-M2) manufactured by Atago Co., Ltd., but is not limited to this method.

In one embodiment of the present invention, the thermoplastic resin composition (C) is
(i) A glass transition temperature measured by a differential scanning calorimeter is 130°C or higher. (ii) A total light transmittance of a 1 mm thick injection molded article is 87% or higher and a haze value is 4% or less. (iii) A refractive index measured by the critical angle method is 1.45 to 1.60.
It may be.

In another embodiment of the present invention, the thermoplastic resin composition (C) is
(i) The glass transition temperature measured by a differential scanning calorimeter may be 149°C or higher and 160°C or lower. (ii) The total light transmittance of an injection molded article having a thickness of 1 mm may be 87% or higher and the haze value may be 4% or lower. (iii) The refractive index measured by a critical angle method may be 1.57 or higher and 1.58 or lower.

In yet another embodiment of the present invention, the thermoplastic resin composition (C) is
(i) The glass transition temperature measured by a differential scanning calorimeter is 140°C or more and less than 149°C. (ii) The total light transmittance of an injection molded article having a thickness of 1 mm is 87% or more and the haze is 4% or less. (iii) The refractive index measured by a critical angle method is 1.56 or more and less than 1.57.

In yet another embodiment of the present invention, the thermoplastic resin composition (C) is
(i) The glass transition temperature measured by a differential scanning calorimeter is 130°C or more and less than 140°C. (ii) The total light transmittance of an injection molded article having a thickness of 1 mm is 87% or more and the haze is 4% or less. (iii) The refractive index measured by a critical angle method is 1.54 or more and less than 1.56.

5. Sheet using thermoplastic resin composition (C) A sheet can be produced using the thermoplastic resin composition (C) of the present invention. In one embodiment of the present invention, the sheet obtained using the thermoplastic resin composition (C) of the present invention may have a total light transmittance of 87% or more when the sheet is 500 μm thick. The sheet obtained using the thermoplastic resin composition (C) of the present invention may have a total light transmittance of 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, etc. when the sheet is 500 μm thick.

6. Film using thermoplastic resin composition (C) A film can be produced using the thermoplastic resin composition (C) of the present invention. In one embodiment of the present invention, the film obtained using the thermoplastic resin composition (C) of the present invention may have a haze value of 4% or less when the film is 50 μm thick. The film obtained using the thermoplastic resin composition (C) of the present invention may have a haze value of 4.0%, 3.5%, 3.0%, 2.5%, 2.0%, 1.5%, 1.0%, 0.5%, 0.3%, 0.1%, 0%, etc. when the film is 50 μm thick.

7. Blend composition (E) with other thermoplastic resin composition (D)
The thermoplastic resin composition (C) of the present invention can be blended with another thermoplastic resin composition (D) to produce a blend composition (E). The thermoplastic resin composition (C) of the present invention and the other thermoplastic resin composition (D) can be blended by a conventional method.

In one embodiment of the present invention, the difference in refractive index between the thermoplastic resin composition (C) and the thermoplastic resin composition (D) measured by the critical angle method may be 0.02 or less. If the difference in refractive index between the thermoplastic resin composition (C) and the thermoplastic resin composition (D) is 0.02 or less, the transparency of the blend composition (E) obtained by blending can be ensured. In one embodiment of the present invention, the difference in refractive index between the thermoplastic resin composition (C) and the thermoplastic resin composition (D) measured by the critical angle method may be, for example, 0.02, 0.01, 0.005, 0.002, 0, etc.

As described above, the other thermoplastic resin composition (D) used to produce the blend composition (E) by blending with the thermoplastic resin composition (C) of the present invention preferably has a refractive index difference of 0.02 or less with the thermoplastic resin composition (C) and does not impair heat resistance. In one embodiment of the present invention, the thermoplastic resin composition (D) may be a thermoplastic resin composition containing at least one thermoplastic resin selected from polyetherester resin, polyamide resin, acrylic resin, polyvinyl chloride resin, and polycarbonate resin.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The methods for synthesizing samples used in the evaluation of the Examples and Comparative Examples and the methods for measuring their physical properties are as follows. The meanings of abbreviations are also described.
DMT: Dimethyl terephthalate TBT: Tetra-n-butyl titanate EG: Ethylene glycol 1,4-CHDM: 1,4-cyclohexanedimethanol SPG: 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane TEP: Triethyl phosphate DOG: 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane

1. Production of polycondensate (B) In the present invention, the polycondensate (B) can be selected from at least one resin selected from the polyester resin (B1), the polycarbonate resin (B2), and the polyester carbonate resin (B3), as described above.

(Production of Polyester Resin (B1-1) (Production Example 1))
DMT (31.7 mol), germanium oxide (0.016 mol), EG solution of TBT (0.0019 mol as TBT), and a mixed solution of 1,4-CHDM and EG (6.5 mol of 1,4-CHDM and 28.1 mol of EG) were charged into a 30 liter (L) polyester production apparatus equipped with a packed column type rectification column, a partial condenser, a total condenser, a cold trap, an agitator, a heating device, and a nitrogen inlet tube. The temperature was raised to 225°C under normal pressure and nitrogen atmosphere to carry out an ester exchange reaction. After the reaction conversion rate of the dicarboxylic acid component was 85 mol% or more, an EG solution of potassium acetate (0.0063 mol as potassium acetate) was added. EG was extracted from the system by reducing the temperature to 185°C and reducing the pressure to 13.3 kPa at the same time. After the pressure was restored, SPG (22.5 mol) was added. The temperature was raised to 225°C and the pressure was gradually reduced to 13.3 kPa to allow the ester exchange reaction to proceed, and the pressure was then restored and TEP (0.098 mol) was added. After the pressure was reduced to 13.3 kPa again, the polycondensation reaction was finally carried out at 280°C and 0.3 kPa or less. The viscosity of the reactant gradually increased, and the reaction was terminated when the appropriate melt viscosity was reached, to obtain the polyester resin (B1-1) of the present invention.

(Production of Polyester Resin (B1-2) (Production Example 2))
A polyester resin (B1-2) was obtained by the same operation as in Production Example 1, except that the amounts of DMT, germanium oxide, EG solution of TBT (0.0018 mol as TBT), mixed solution of 1,4-CHDM and EG (6.3 mol of 1,4-CHDM, 25.7 mol of EG), EG solution of potassium acetate (0.0061 mol as potassium acetate), SPG, and TEP were changed to 30.7 mol, 0.015 mol, and 0.0018 mol, respectively.

(Production of Polyester Resin (B1-3) (Production Example 3))
DMT (1.1 mol), germanium oxide (0.00055 mol), EG solution of TBT (0.00007 mol as TBT), and a mixed solution of 1,4-CHDM and EG (0.22 mol of 1,4-CHDM, 0.97 mol of EG) were charged into a 1 liter (L) polyester production apparatus equipped with a packed column type rectification column, a partial condenser, a cold trap, an agitator, a heating device, and a nitrogen inlet tube. The temperature was raised to 225°C under normal pressure and nitrogen atmosphere to carry out an ester exchange reaction. After the reaction conversion rate of the dicarboxylic acid component was increased to 70 mol% or more, an EG solution of potassium acetate (0.0002 mol as potassium acetate) was added. EG was extracted from the system by reducing the temperature to 185°C and reducing the pressure to 13.3 kPa at the same time. After the pressure was restored, SPG (0.72 mol) was added. The temperature was raised to 225°C and the pressure was gradually reduced to 13.3 kPa to allow the ester exchange reaction to proceed, and the pressure was then restored and TEP (0.0034 mol) was added. After the pressure was reduced to 13.3 kPa again, the polycondensation reaction was finally carried out at 280°C and 0.3 kPa or less. The viscosity of the reactant gradually increased, and the reaction was terminated when the appropriate melt viscosity was reached, to obtain the polyester resin (B1-3) of the present invention.

(Production of Polyester Resin (B1-4) (Production Example 4))
DMT (1.0 mol), DOG (0.21 mol), germanium oxide (0.00051 mol), EG solution of TBT (0.00006 mol as TBT), and EG (0.90 mol) were charged into a 1 liter (L) polyester production apparatus equipped with a packed column type rectification column, a partial condenser, a cold trap, an agitator, a heating device, and a nitrogen inlet tube. The temperature was raised to 225°C under normal pressure and nitrogen atmosphere to carry out an ester exchange reaction. After the reaction conversion rate of the dicarboxylic acid component was set to 70 mol% or more, an EG solution of potassium acetate (0.0002 mol as potassium acetate) was added. EG was extracted from the system by reducing the temperature to 185°C and reducing the pressure to 13.3 kPa at the same time. After the pressure was restored, SPG (0.72 mol) was added. The temperature was raised to 225°C and the pressure was gradually reduced to 13.3 kPa to allow the ester exchange reaction to proceed, and the pressure was then restored and TEP (0.0031 mol) was added. After the pressure was reduced to 13.3 kPa again, the polycondensation reaction was finally carried out at 280°C and 0.3 kPa or less. The viscosity of the reactant gradually increased, and the reaction was terminated when the appropriate melt viscosity was reached, to obtain polyester resin (B1-4) of the present invention.

(Production of Polyester Resin (B1-5) (Production Example 5))
DMT (1.0 mol), germanium oxide (0.00052 mol), EG solution of TBT (0.00006 mol as TBT), DOG (0.11 mol), and a mixed solution of 1,4-CHDM and EG (0.14 mol of 1,4-CHDM, 0.92 mol of EG) were charged into a 1 liter (L) polyester production apparatus equipped with a packed column type rectification column, a partial condenser, a cold trap, an agitator, a heating device, and a nitrogen inlet tube. The temperature was raised to 225°C under normal pressure and nitrogen atmosphere to carry out an ester exchange reaction. After the reaction conversion rate of the dicarboxylic acid component was set to 70 mol% or more, an EG solution of potassium acetate (0.0002 mol as potassium acetate) was added. EG was extracted from the system by reducing the temperature to 185°C and reducing the pressure to 13.3 kPa at the same time. After the pressure was restored, SPG (0.74 mol) was added. The temperature was raised to 225°C and the pressure was gradually reduced to 13.3 kPa to allow the ester exchange reaction to proceed, and the pressure was then restored and TEP (0.0032 mol) was added. After the pressure was reduced to 13.3 kPa again, the polycondensation reaction was finally carried out at 280°C and 0.3 kPa or less. The viscosity of the reactant gradually increased, and the reaction was terminated when the appropriate melt viscosity was reached, to obtain the polyester resin (B1-5) of the present invention.

(Production of Polyester Resin (B1-6) (Production Example 6))
DMT (1.5 mol), germanium oxide (0.00073 mol), EG solution of TBT (0.00009 mol as TBT), and a mixed solution of 1,4-CHDM and EG (0.15 mol of 1,4-CHDM and 1.47 mol of EG) were charged into a 1 liter (L) polyester production apparatus equipped with a packed column type rectification column, a partial condenser, a cold trap, an agitator, a heating device, and a nitrogen inlet tube. The temperature was raised to 225°C under normal pressure and nitrogen atmosphere to carry out an ester exchange reaction. After the reaction conversion rate of the dicarboxylic acid component was increased to 70 mol% or more, an EG solution of potassium acetate (0.0003 mol as potassium acetate) was added. EG was extracted from the system by reducing the temperature to 185°C and reducing the pressure to 13.3 kPa at the same time. After the pressure was restored, SPG (0.45 mol) was added. The temperature was raised to 225°C and the pressure was gradually reduced to 13.3 kPa to allow the ester exchange reaction to proceed, and the pressure was then restored and TEP (0.0045 mol) was added. After the pressure was reduced to 13.3 kPa again, the polycondensation reaction was finally carried out at 280°C and 0.3 kPa or less. The viscosity of the reactant gradually increased, and the reaction was terminated when the appropriate melt viscosity was reached, to obtain the polyester resin (B1-6) of the present invention.

(Production of Polycarbonate Resin (B2-1) (Production Example 7))
2 kg (6.57 mol) of spiroglycol, 643 g (2.82 mol) of bisphenol A, 2.1 kg (9.72 mol) of diphenyl carbonate, and 0.0047 g (5.6×10 ⁻⁵ mol) of sodium hydrogen carbonate were placed in a 10-liter reactor equipped with a stirrer and a distillation device, and heated to 215° C. for 1 hour under a nitrogen atmosphere of 150 Torr and stirred. Then, the mixture was held for 20 minutes under conditions of 215° C. and 150 Torr to carry out an ester exchange reaction. The mixture was further heated to 230° C. over 10 minutes, and held for 1 hour under conditions of 230° C. and 150 Torr to carry out an ester exchange reaction. The mixture was then heated to 240° C. over 10 minutes, and the ester exchange reaction was carried out at 240° C. for 50 minutes. Then, the mixture was adjusted to 100 Torr over 10 minutes, and held at 240° C. and 100 Torr for 20 minutes. The pressure was then adjusted to 40 Torr over 10 minutes, and the mixture was maintained at 240° C. and 40 Torr for 30 minutes. The pressure was then reduced to 1 Torr or less over 20 minutes, and the polymerization reaction was carried out under stirring for 1 hour under conditions of 240° C. and 1 Torr or less. After the reaction was completed, nitrogen was blown into the reactor to apply pressure, and the produced resin was pelletized and withdrawn to obtain polycarbonate resin (B2-1).

(Production of Polycarbonate Resin (B2-2) (Production Example 8))
A polycarbonate resin (B2-2) was obtained in the same manner as in Production Example 7, except that the amounts of spiroglycol, bisphenol A, diphenyl carbonate, and sodium hydrogen carbonate were 1.5 kg (4.9 mol), 1.12 kg (4.9 mol), 2.2 kg (10.2 mol), and 0.0050 g (5.9× ¹⁰ mol), respectively.

(Production of Polycarbonate Resin (B2-3) (Production Example 9))
A polycarbonate resin (B2-3) was obtained in the same manner as in Production Example 7, except that the amounts of spiroglycol, bisphenol A, diphenyl carbonate, and sodium hydrogen carbonate were 300 g (0.99 mol), 2.02 kg (8.87 mol), 2.2 kg (10.2 mol), and 0.0050 g (5.9 × ^10-5 mol), respectively.

(Production of Polycarbonate Resin (B2-4) (Production Example 10))
A polycarbonate resin (B2-4) was obtained by the same operation as in Production Example 7, except that the amounts of spiroglycol, 1,200 g (3.9 mol), bisphenol A, 1.5 kg (6.6 mol), diphenyl carbonate, 2.9 kg (13.6 mol), and sodium hydrogen carbonate were changed to 0.0066 g (7.9 × ^10-5 mol), and 380 g (2.6 mol) of 1,4-CHDM were added at the same time.

(Production of Polycarbonate Resin (B2-5) (Production Example 11))
A polycarbonate resin (B2-5) was obtained by the same operation as in Production Example 7, except that the amounts of spiro glycol, 1200 g (3.9 mol), bisphenol A, 1.5 kg (6.6 mol), diphenyl carbonate, 2.9 kg (13.6 mol), and sodium hydrogen carbonate were changed to 0.0066 g (7.9× ¹⁰ mol), and 570 g (2.6 mol) of DOG were added at the same time.

(Production of Polycarbonate Resin (B2-6) (Production Example 12))
A polycarbonate resin (B2-6) was obtained by the same operation as in Production Example 7, except that 1200 g (3.9 mol) of spiro glycol, 1.5 kg (6.6 mol) of bisphenol A, 2.9 kg (13.6 mol) of diphenyl carbonate, and 0.0066 g (7.9× ¹⁰ mol) of sodium hydrogen carbonate were used, and 190 g (1.3 mol) of 1,4-CHDM and 290 g (1.3 mol) of DOG were added at the same time.

(Production of Polycarbonate Resin (B2-7) (Production Example 13))
A polycarbonate resin (B2-7) was obtained by the same procedure as in Production Example 7, except that 948 g (6.6 mol) of 1,4-CHDM, 1.5 kg (6.6 mol) of bisphenol A, 2.9 kg (13.6 mol) of diphenyl carbonate, and 0.0066 g (7.9 × ¹⁰ mol) of sodium hydrogen carbonate were used instead of spiro glycol.

(Production of Polyester Carbonate Resin (B3-1) (Production Example 14))
A 1-liter reactor equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube was charged with 300 g (0.99 mol) of SPG, 96 g (0.29 mol) of DMT, 41 g (0.20 mol) of dimethyl 1,4-cyclohexanedicarboxylate, and 0.08 g of dibutyltin oxide, and reacted for 6 hours at a temperature of 180 to 230°C under a nitrogen atmosphere to distill off methanol. The terminal hydroxyl value of the resulting prepolymer was 3.0. Next, 57 g (0.26 mol) of diphenyl carbonate was added to 300 g of the prepolymer, and the reaction was carried out for 5 hours at a temperature of 230 to 240°C, finally at a reduced pressure of 1 mmHg. After the reaction was completed, nitrogen was blown into the reactor to apply pressure, and the resulting resin was pelletized and extracted to obtain polyester carbonate resin (B3-1).

(Production of Polyester Carbonate Resin (B3-2) (Production Example 15))
A 1-liter reactor equipped with a stirrer, a distillation condenser, a thermometer, and a gas inlet tube was charged with 300 g (0.99 mol) of SPG, 47 g (0.33 mol) of CHDM, 128 g (0.66 mol) of DMT, and 0.09 g of dibutyltin oxide, and reacted for 6 hours at a temperature of 180 to 230 ° C. under a nitrogen atmosphere to distill off methanol. The terminal hydroxyl value of the resulting prepolymer was 2.8. Next, 53 g (0.25 mol) of diphenyl carbonate was added to 300 g of the prepolymer, and the reaction was carried out for 5 hours at a temperature of 230 to 240 ° C., finally at a reduced pressure of 1 mmHg. After the reaction was completed, nitrogen was blown into the reactor to apply pressure, and the resulting resin was pelletized and extracted to obtain polyester carbonate resin (B3-2).

(Production of Polyester Carbonate Resin (B3-3) (Production Example 16))
A 1-liter reactor equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube was charged with 300 g (0.99 mol) of SPG, 95 g (0.66 mol) of CHDM, 160 g (0.82 mol) of DMT, and 0.11 g of dibutyltin oxide, and reacted for 6 hours at a temperature of 180 to 230 ° C. under a nitrogen atmosphere to distill off methanol. The terminal hydroxyl value of the resulting prepolymer was 3.0. Next, 57 g (0.26 mol) of diphenyl carbonate was added to 300 g of the prepolymer, and the reaction was carried out for 5 hours at a temperature of 230 to 240 ° C., finally at a reduced pressure of 1 mmHg. After the reaction was completed, nitrogen was blown into the reactor to apply pressure, and the resulting resin was pelletized and extracted to obtain a polyester carbonate resin (B3-3).

(Production of Polyester Carbonate Resin (B3-4) (Production Example 17))
A 1-liter reactor equipped with a stirrer, a distillation condenser, a thermometer, and a gas inlet tube was charged with 100 g (0.69 mol) of CHDM, 129 g (2.1 mol) of EG, 270 g (1.4 mol) of DMT, and 0.09 g of dibutyltin oxide, and reacted for 6 hours at a temperature of 180 to 230 ° C. under a nitrogen atmosphere to distill off methanol. The terminal hydroxyl value of the resulting prepolymer was 3.1. Next, 59 g (0.27 mol) of diphenyl carbonate was added to 300 g of the prepolymer, and the reaction was carried out for 5 hours at a temperature of 230 to 240 ° C., finally at a reduced pressure of 1 mmHg. After the reaction was completed, nitrogen was blown into the reactor to apply pressure, and the resulting resin was pelletized and extracted to obtain polyester carbonate resin (B3-4).

(Evaluation of Polycondensate (B))
The polycondensate (B) was evaluated by the following methods. The evaluation results are shown in Tables 1, 2 and 3.

(1) Diol units having a cyclic acetal skeleton and alicyclic diol units in the diol constituent units of the polycondensate The diol units having a cyclic acetal skeleton and alicyclic diol units in the diol constituent units of the polycondensate were calculated by 1H-NMR measurement. The measurement was performed at 500 MHz using an AVANCEIII500 manufactured by BRUKER. Deuterated chloroform was used as the solvent.

(2) Glass Transition Temperature The glass transition temperature (Tg) of the polycondensate was measured by placing about 10 mg of a sample in an aluminum non-sealed container in a nitrogen gas (50 ml/min) flow at a temperature rise rate of 20° C./min using a DSC/TA-50WS manufactured by Shimadzu Corporation. The glass transition temperature was determined as the temperature at which the temperature changed by half the difference in the baseline before and after the transition of the DSC curve.

In addition, in Tables 1, 2, and 3, 1,4-cyclohexanedimethanol is abbreviated as "CHDM", 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane is abbreviated as "SPG", 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane is abbreviated as "DOG", and bisphenol A is abbreviated as "BPA".

Product 1 used was a polyester resin manufactured by Mitsubishi Gas Chemical Company, Inc. (product name: ALTESTER (registered trademark) "S3000", diol component copolymerization ratio: SPG 30 mol%, EG 70 mol%, Tg: 103°C).

For product 2, we used polyester resin manufactured by Eastman Chemical Company (product name: EASTAR (registered trademark) "GN001", diol component copolymerization ratio: CHDM 43 mol%, EG 57 mol%, Tg: 83°C).

[Examples 1 to 84, Comparative Examples 1 to 12]
As the polycarbonate resins, (A-1): polycarbonate resin (product name: Iupilon (registered trademark) S-3000) manufactured by Mitsubishi Engineering Plastics Corporation, (A-2): polycarbonate resin (product name: Iupilon (registered trademark) H-4000) manufactured by Mitsubishi Engineering Plastics Corporation, and (A-3): polycarbonate resin (product name: Iupilon (registered trademark) E-2000) manufactured by Mitsubishi Engineering Plastics Corporation were used.

2. Preparation of Thermoplastic Resin Composition (C) The polycarbonate resin (A) and polycondensate (B) in the amounts shown in Tables 5 to 24 were mixed in a tumbler. This resin mixture was melt-mixed using a twin-screw extruder (screw diameter: 20 mm, L/D: 25) under conditions of a cylinder temperature of 265 to 285°C, a die temperature of 265 to 285°C, and a screw rotation speed of 50 rpm.

3. Preparation of injection molded articles Thermoplastic resin composition (C) was molded into various test pieces having a thickness of 1.0 mm using a screw-type injection molding machine (screw diameter: 28 mm, mold clamping force: 490 kN) under conditions of a cylinder temperature of 260 to 280°C and a mold temperature of 30 to 70°C.

4. Preparation of Sheet The thermoplastic resin composition (C) was extruded into a 500 μm thick sheet by a T-die method using a twin-screw extruder (screw diameter: 29.75 mm, L/D: 30) under conditions of a cylinder temperature of 265 to 285° C., a T-die temperature of 265 to 285° C., and a screw rotation speed of 50 rpm.

5. Preparation of Film The 500 μm thick sheet prepared under the conditions described above was subjected to simultaneous biaxial stretching at 3.0×3.0 times at a temperature 10 to 20° C. higher than the glass transition temperature of the thermoplastic resin composition (C) to prepare a 50 μm thick film.

[Evaluation method]
The resin compositions of Examples 1 to 84 and Comparative Examples 1 to 12 were evaluated as follows. The evaluation results are summarized in Tables 5 to 24.

(1) Haze and total light transmittance: A 1.0 mm thick injection molded article, a 500 μm thick sheet, and a 50 μm thick film were used in accordance with JIS K7105. The measuring device used was a color and turbidity simultaneous measuring instrument (model: COH-400) manufactured by Nippon Denshoku Industries Co., Ltd.

(2) Refractive index: Measurement was performed using an injection molded article having a thickness of 1.0 mm in accordance with JIS K7142. The measuring device used was a multi-wavelength Abbe refractometer (model: DR-M2) manufactured by Atago Co., Ltd.

Example 85
(1) Measurement of refractive index of thermoplastic resin composition (D)
As the thermoplastic resin composition (D), (D-1): polyether ester resin (trade name: ELECUT (registered trademark) R02) manufactured by Takemoto Oil & Fat Co., Ltd. was used. This was molded into a 1.0 mm thick test piece using a screw-type injection molding machine (screw diameter: 28 mm, mold clamping force: 490 kN) under conditions of a cylinder temperature of 260°C and a mold temperature of 50°C. The refractive index of the molded product thus produced was measured in accordance with JIS K7142 using a multi-wavelength Abbe refractometer (model: DR-M2) manufactured by Atago Co., Ltd. The refractive index value obtained was 1.560.

(2) Preparation of thermoplastic resin composition (C) Polycarbonate resin (A) (A-1): 60 wt% polycarbonate resin (trade name: Iupilon (registered trademark) S-3000) manufactured by Mitsubishi Engineering Plastics Co., Ltd., and 40 wt% B1-1 (Table 1, Production Example 1) as polycondensate (B) were mixed by a tumbler. This resin mixture was melt-mixed using a twin-screw extruder (screw diameter: 20 mm, L/D: 25) under conditions of cylinder temperature 265 ° C., die temperature 265 ° C., and screw rotation speed 50 rpm to obtain a thermoplastic resin composition (C-6) (Table 5). Subsequently, a screw-type injection molding machine (screw diameter: 28 mm, mold clamping force: 490 kN) was used to mold a 1.0 mm thick test piece under conditions of cylinder temperature 265 ° C. and mold temperature 50 ° C. The refractive index of the produced molded product was measured in accordance with JIS K7142 using a multi-wavelength Abbe refractometer (model: DR-M2) manufactured by Atago Co., Ltd. The obtained refractive index value was 1.560.

(3) Preparation of injection molded articles from blend composition (E) 20 wt % of the thermoplastic resin composition (D-1) and 80 wt % of the thermoplastic resin composition (C-6) were mixed in a tumbler. This resin mixture was molded into various test pieces having a thickness of 1.0 mm using a screw-type injection molding machine (screw diameter: 28 mm, mold clamping force: 490 kN) under conditions of a cylinder temperature of 265°C and a mold temperature of 50°C.

[Evaluation method]
The blend composition of Example 85 was evaluated as follows. The evaluation results are shown in Table 25.

(1) Haze and total light transmittance: Measurements were carried out using an injection molded article having a thickness of 1.0 mm in accordance with JIS K7105. The measuring device used was a color and turbidity simultaneous measuring instrument (model: COH-400) manufactured by Nippon Denshoku Industries Co., Ltd.

(2) Refractive index: Measurement was performed using an injection molded article having a thickness of 1.0 mm in accordance with JIS K7142. The measuring device used was a multi-wavelength Abbe refractometer (model: DR-M2) manufactured by Atago Co., Ltd.

As described above, the thermoplastic resin composition (C) of the present invention and the blend composition (E) with another thermoplastic resin composition (D) can not only adjust the refractive index of the polycarbonate resin even with a smaller alloy ratio while maintaining the transparency of the polycarbonate resin, but also have high heat resistance.

Claims (8)

A thermoplastic resin composition (C) comprising a polycarbonate resin (A) and a polycondensate (B),
The thermoplastic resin composition (C) contains 40 to 99% by weight of the polycarbonate resin (A) and 60 to 1% by weight of the polycondensate (B); and
The polycondensate (B) is selected from a polyester resin (B1), a polycarbonate resin (B2), or a polyester carbonate resin (B3),
The polyester resin (B1) contains, in its diol constituent units,
(i) 65 to 75 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) containing 0 to 20 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton and/or an alicyclic diol (b2);
The polycarbonate resin (B2) contains, in its diol constituent units,
(i) 10 to 30 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
(ii) 0 to 20 mol % of a diol (b1) having a non-spiro ring-containing cyclic acetal skeleton and/or an alicyclic diol (b2) ,
(iii) containing 50 to 90 mol % bisphenol A ;
The polyester carbonate resin (B3) contains, in its diol constituent units,
(i) containing 60 to 100 mol % of a diol (a1) having a spiro ring-containing cyclic acetal skeleton,
The polycarbonate resin (A) is a polycarbonate ester of bisphenol,
the diol component (a1) having a spiro ring-containing cyclic acetal skeleton is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
the diol component (b1) having a non-spiro ring-containing cyclic acetal skeleton is 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane,
the alicyclic diol (b2) is 1,4-cyclohexanedimethanol,
the dicarboxylic acid constituent unit of the polyester resin (B1) is a dicarboxylic acid unit selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue,
The dicarboxylic acid constituent unit of the polyester carbonate (B3) contains an alicyclic dicarboxylic acid or a diester thereof (b3),
The thermoplastic resin composition (C), wherein the alicyclic dicarboxylic acid or its diester (b3) is 1,4-cyclohexanedicarboxylic acid or dimethyl 1,4-cyclohexanedicarboxylate . The thermoplastic resin composition (C) according to claim 1 , wherein the bisphenol is selected from the group consisting of bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD and bisphenol MIBK. The polyester resin (B1) contains , in its diol constituent units,
The diol (a1) having a spiro ring - containing cyclic acetal skeleton,
The diol (b1) having a non - spiro ring-containing cyclic acetal skeleton, and
The alicyclic diol (b2)
The thermoplastic resin composition (C) according to claim 1 or 2 , comprising: The thermoplastic resin composition (C) according to any one of claims 1 to 3 , having the following physical properties (i) to (iii):
(i) A glass transition temperature measured by a differential scanning calorimeter is 130°C or higher. (ii) A total light transmittance of a 1 mm thick injection molded article is 87% or higher and a haze value is 4% or less. (iii) A refractive index measured by the critical angle method is 1.45 to 1.60. A sheet obtained by using the thermoplastic resin composition (C) according to any one of claims 1 to 4 , which has a total light transmittance of 87% or more when it is 500 µm thick. A film obtained by using the thermoplastic resin composition (C) according to any one of claims 1 to 4 , the haze of which when measured at a thickness of 50 µm is 4% or less. A blend composition (E) of the thermoplastic resin composition (C) according to any one of claims 1 to 4 and a thermoplastic resin composition (D), wherein the difference in refractive index between the thermoplastic resin composition (C) and the thermoplastic resin composition (D) measured by a critical angle method is 0.02 or less. The blend composition (E) according to claim 7, wherein the thermoplastic resin composition (D) is a thermoplastic resin composition containing at least one thermoplastic resin selected from a polyetherester resin, a polyamide resin, an acrylic resin, a polyvinyl chloride resin, and a polycarbonate resin.