RESIN COMPOSITION, OPTICAL LENS CONTAINING THIS, AND OPTICAL FILM

Abstract

A resin composition contains: a resin containing a constituent unit (A) represented by general formula (1); and a resin containing a constituent unit (B) represented by formula (2) and/or a constituent unit (C) represented by formula (3). (R.sub.1 represents a methyl group or an ethyl group, R.sub.2 and R.sub.3 represent a hydrogen atom or a methyl group, and n represents 0 or 1.) (R.sub.a and R.sub.b represent a hydrogen atom, etc., R.sub.h represents an aryl group of 6-20 carbons, X represents a single bond or a fluorene group, A and B represent an alkylene group of 1-4 carbons, m and n represent integers 0-6, and a and b represent integers 0-10.) (R.sub.c and R.sub.d represent a hydrogen atom, etc., Y represents a fluorene group, A and B represent an alkylene group of 1-4 carbons, p and q represent integers 0-4, and a and b represent integers 0-10.)

##STR00001##

Claims

1. A resin composition comprising: a resin containing a structural unit (A) represented by General formula (1) below; and a resin containing a structural unit (B) represented by General formula (2) below and/or a structural unit (C) represented by General formula (3) below: ##STR00034## in General formula (1), R.sub.1 represents a hydrogen atom, a methyl group or an ethyl group, R.sub.2 and R.sub.3 each independently represent a hydrogen atom or a methyl group, and n represents 0 or 1; ##STR00035## in General formula (2), R.sub.a and R.sub.b are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxyl group, a C6-C20 aryl group, a C6-C20 heteroaryl group or a C6-C20 aryloxy group containing one or more heteroatoms selected from O, N and S, and —C≡C—R.sub.h, R.sub.h represents a C6-C20 aryl group or a C6-C20 heteroaryl group containing one or more heteroatoms selected from O, N and S, X represents a single bond or a fluorene group, A and B each independently represent a C1-C4 alkylene group, m and n each independently represent an integer from 0 to 6, and a and b each independently represent an integer from 0 to 10; ##STR00036## in General formula (3), R.sub.c and R.sub.d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxyl group, and a C6-C20 aryl group, Y represents a fluorene group, A and B each independently represent a C1-C4 alkylene group, p and q each independently represent an integer from 0 to 4, and a and b each independently represent an integer from 0 to 10.

2. The resin composition according to claim 1, wherein the resin containing the structural unit (A) represented by General formula (1) above is a polyester resin, and the resin containing the structural unit (B) represented by General formula (2) above and/or the structural unit (C) represented by General formula (3) above is a polycarbonate resin.

3. The resin composition according to claim 1, further comprising a resin containing a structural unit (D) represented by General formula (4) below: ##STR00037## in General formula (4), R.sub.4 represents a hydrogen atom, a methyl group, or an ethyl group, and R.sub.5 and R.sub.6 each independently represent a hydrogen atom or a methyl group.

4. The resin composition according to claim 3, wherein the resin containing the structural unit (D) represented by General formula (4) above is a polycarbonate resin.

5. The resin composition according to claim 1, wherein the structural unit (B) represented by General formula (2) above comprises at least one of structural units represented by General formulae (2a) and (2b) below: ##STR00038## in General formula (2a), R.sub.a, R.sub.b, A, B, a, and b are synonymous with those in General formula (2), respectively; ##STR00039## in General formula (2b), A, B, a, and b are synonymous with those in General formula (2), respectively; and R.sub.e and R.sub.f are each independently selected from the group consisting of a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxyl group, a C6-C20 aryl group, and a C6-C20 aryloxy group.

6. The resin composition according to claim 1, wherein R.sub.a and R.sub.b in General formula (2) above each independently represent a hydrogen atom, a phenyl group, a naphthyl group, or a substituent selected from the group consisting of the following: ##STR00040##

7. The resin composition according to claim 1, wherein the structural unit (C) represented by General formula (3) above comprises a structural unit represented by General formula (3a) below: ##STR00041## in General formula (3a), A, B, a, and b are synonymous with those in General formula (3), respectively; and R.sub.e and R.sub.f are each independently selected from the group consisting of a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxyl group, a C6-C20 aryl group, and a C6-C20 aryloxy group.

8. The resin composition according to claim 1, wherein a mass ratio (AB) of the structural unit (A) to the structural unit (B) is 99/1 to 1/99.

9. The resin composition according to claim 1, wherein a mass ratio (A/C) of the structural unit (A) to the structural unit (C) is 99/1 to 1/99.

10. The resin composition according to claim 3, wherein a mass ratio (A/D) of the structural unit (A) to the structural unit (D) is 99/1 to 1/99.

11. The resin composition according to claim 1, further comprising an antioxidant.

12. The resin composition according to claim 11, wherein the antioxidant is a phosphite antioxidant and/or a phenolic antioxidant.

13. The resin composition according to claim 1, wherein R.sub.1, R.sub.2, and R.sub.3 in General formula (1) above represent hydrogen atoms, and n represents 1.

14. A molded body comprising the resin composition according to claim 1.

15. The molded body according to claim 14, wherein the molded body is an optical lens.

16. The molded body according to claim 14, wherein the molded body is an optical film.

Description

EXAMPLES

[0153] Hereinafter, the present invention will be described by way of examples, although the present invention should not be limited in any way to these examples. The measurements in the examples were made using the following methods and equipment.

<Evaluation Methods for Polyester Resin, Polycarbonate Resin, and Resin Composition>

[0154] (1) Copolymer composition of polyester resin

[0155] .sup.1H-NMR and .sup.13C-NMR were measured to calculate the copolymer composition of the polyester resin from the peak area ratio derived from each structural unit. The measurement was performed using a nuclear magnetic resonance spectrometer (product name AVANCE III 500/Ascend 500, manufactured by Bruker BioSpin Corporation) at 500 MHz. Deuterated chloroform was used as the solvent.

(2) Weight average molecular weight (Mw)

[0156] The weight average molecular weights of the resins and the resin composition were measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene. The instrument, columns, and measurement conditions used were as follows. [0157] GPC instrument: HLC-8420GPC manufactured by Tosoh Corporation [0158] Columns TSKgel SuperHM-M (×3 columns) manufactured by Tosoh Corporation TSKgel guard column SuperH-H (×1 column) manufactured by Tosoh Corporation [0159] TSKgel SuperH-RC (×1 column) manufactured by Tosoh Corporation [0160] Detector: RI detector [0161] Standard polystyrenes: Standard polystyrene kit PStQuick C manufactured by Tosoh Corporation [0162] Sample solution: 0.2 Mass % tetrahydrofuran solution [0163] Eluent: Tetrahydrofuran [0164] Flow rate of eluent: 0.6 mL/min [0165] Column temperature: 40° C.
(3) Glass transition temperature (Tg)

[0166] The glass transition temperatures of the resins and the resin composition were measured using a differential scanning calorimeter (product name: DSC-60/TA-60WS, manufactured by Shimadzu Corporation). 5-10 mg of the sample was placed in an unsealed aluminum container, and the temperature was increased to 280° C. at a rate of 10° C./min in a stream of nitrogen gas (50 mL/min), followed by rapid cooling. The temperature was again increased under the same conditions, and the temperature at which the DSC curve changed by half the difference in the baseline before and after the transition (midpoint glass transition temperature) was used as the glass transition temperature.

(4) Refractive index (nd) and Abbe number (vd)

[0167] The refractive indices and Abbe numbers of the resins and the resin composition were measured by cutting out a measurement sample at right angle from the center of a 44 mm diameter, 3 mm thick disk-shaped molded body produced by the method described below. The sample was annealed in a dryer at 100° C. for 12 hours and then subjected to measurement using a precision refractometer (KPR-200 manufactured by Kalnew Optical Industrial Co., Ltd.) The refractive indices were measured at a temperature of 23° C. and wavelengths of 486.1 nm (F line), 587.6 nm (d line), and 656.3 nm (C line). The Abbe number was calculated from the refractive indices at these wavelengths using the following Formula (1).

vd=(nd−1)/(nF-nC)  Formula(1)

[0168] (In Formula (1), vd is the Abbe number, nF is the refractive index at the wavelength of 486.1 nm, nd is the refractive index at the wavelength of 587.6 nm, and nC is the refractive index at the wavelength of 656.3 nm.)

(5) Preparation of disk-shaped molded body (diameter: 44 mm, thickness: 3 mm)

[0169] Injection molding was performed using an injection molding machine (J55AD manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 260-270° C. and a mold temperature of 110-120° C. to produce a disk-shaped molded body of the resin composition.

(6) Continuous formability

[0170] Injection molding was continuously performed using an injection molding machine (ROBOSHOT α-S30iA manufactured by Fanuc Corporation) and a mold that can form eight aspherical lenses with an outer diameter of 4.7 mm and a center thickness of 0.26 mm, under the following conditions: cylinder temperature of 290° C., mold temperature of [Tg-10° C.], and molding cycle time of 25 to 40 sec/shot. If any of the lens part, sprue, or runner was damaged during molding, continuous molding was terminated at that point, where continuous moldability was evaluated based on the following criteria.

[0171] A: Continuous molding capacity of 30 shots or more

[0172] B: Continuous molding capacity of less than 30 shots, with a small degree of visual damage

[0173] B′: Continuous molding capacity of less than 30 shots, with a large degree of visual damage

<Synthesis of Polyester Resin>

Synthesis Examples 1-4

[0174] Raw monomers and manganese(II) acetate tetrahydrate in the quantities indicated in Table 1 below were supplied in a 30 L reactor equipped with a stirrer, a heater, a nitrogen inlet tube, a partial condenser, a total condenser, a cold trap, and a vacuum pump, and transesterification reaction was conducted in a nitrogen atmosphere by increasing the temperature to 235-245° C. and by stirring. After the reaction conversion of the hydroxycarboxylic acid ester component and the diester component became 90% or higher as calculated from the amount of methanol distilled from the reactor, germanium(IV) oxide and phosphoric acid were added in the amounts indicated in Table 1 below, and the polycondensation reaction was conducted at 270-280° C. and 133 Pa or lower by gradually increasing the temperature and reducing the pressure. Once the reaction solution was confirmed to have reached an appropriate melt viscosity, stirring was stopped, nitrogen was blown into the reactor to increase the pressure to 0.3 MPa, and the resulting polyester resin was collected while pelletizing. The evaluation results of the obtained polyester resins are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Synthesis Synthesis Synthesis Synthesis example 1 Example 2 Example 3 Example 4 Polymerization of polyester resin Monomer feed Hydroxycarboxylic D-NHEs 17.28 14.60 13.30 14.85 [kg] acid ester Diester DMCD 0.94 1.84 2.28 0 FDPM 0 0 0 2.51 Diol BPEF 0 1.68 2.50 0.65 EG 2.73 3.19 2.24 2.67 Amount of Manganese(II) acetate 2.15 3.57 6.42 3.56 polymerization tetrahydrate catalyst added [g] Germanium(IV) oxide 11.53 11.53 11.53 11.52 Amount of heat Phosphoric acid 2.53 4.05 3.80 4.05 stabilizer added [g] Evaluation results Copolymer Hydroxycarboxylic D-NHEs 86 75 70 81 composition acid unit = Unit (A) [mol %] Dicarboxylic acid DMCD 7 12.5 15 0 unit = Unit (C) FDPM 0 0 0 9.5 Diol unit = BPEF 0 5 7 2 Unit (B) EG 7 7.5 8 7.5 Weight average molecular weight (Mw) 31000 34000 39000 35000 Glass transition temperature (Tg) [° C.] 152 147 143 148 Refractive index (nd) 1.54 1.55 1.55 1.55 Abbe number (vd) 56.0 47.7 44.5 45.0 [00027][00028][00029][00030][00031]

<Synthesis of Polycarbonate Resin>

Synthesis Example 5

[0175] 20.00 kg (45.61 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 10.16 kg (47.43 mol) of diphenyl carbonate (DPC), and 30.00 mg (3.6×10.sup.−4 mol) of sodium hydrogen carbonate were placed in a 50 L reactor equipped with a stirrer and a distillation unit and heated to 205° C. spending 60 minutes in a nitrogen atmosphere at 760 Torr and stirred. The pressure was then reduced to 200 Torr spending 20 minutes and held at 205° C. and 200 Torr for 30 minutes. Subsequently, the temperature was increased and the pressure was decreased to 215° C. and 180 Torr, respectively, spending 20 minutes, then to 230° C. and 150 Torr spending 50 minutes, further to 240° C. and 1 Torr or lower spending 60 minutes, and finally held at 240° C. and 1 Torr or lower for 20 minutes. Once the reaction solution was confirmed to have reached an appropriate melt viscosity, stirring was stopped, nitrogen was blown into the reactor to increase the pressure, and the resulting polycarbonate resin was collected while pelletizing.

[0176] The resulting polycarbonate resin had a polystyrene-equivalent weight average molecular weight (Mw) of 23,000 and a glass transition temperature (Tg) of 145° C.

[0177] BPEF: 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (bisphenoxyethanol fluorene)

##STR00032##

Synthetic Example 6

[0178] 23.50 kg (105.70 mol) of decahydro-1,4:5,8-dimethanonaphthalene-2,6(7)-dimethanol (also referred to as “D-NDM”) represented by Structural formula (a) below, 22.98 kg (107.27 mol) of diphenyl carbonate (also referred to as “DPC”), and 130.00 mg (1.5×10.sup.−3 mol) of sodium hydrogen carbonate were placed in a 50 L reactor equipped with a stirrer and a distillation unit and heated to 205° C. spending 60 minutes in a nitrogen atmosphere at 760 Torr and stirred. Then, the pressure was reduced to 200 Torr spending 30 minutes and held at 205° C. and 200 Torr for 30 minutes. Subsequently, the temperature was increased and the pressure was decreased to 215° C. and 180 Torr, respectively, spending 20 minutes, then to 230° C. and 150 Torr spending 40 minutes, further to 240° C. and 1 Torr or lower spending 60 minutes, and finally held at 240° C. and 1 Torr or lower for 20 minutes. Once the reaction solution was confirmed to have reached an appropriate melt viscosity, stirring was stopped, nitrogen was blown into the reactor to increase the pressure, and the resulting polycarbonate resin was collected while pelletizing.

[0179] The resulting polycarbonate resin had a polystyrene-equivalent weight average molecular weight (Mw) of 27,000 and a glass transition temperature (Tg) of 132° C.

[0180] D-NDM: Decahydro-1,4:5,8-dimethanonaphthalene-2,6(7)-dimethanol

##STR00033##

<Method for Producing Resin Composition>

Examples 1-8 and Comparative Examples 1-4

[0181] The polyester resins obtained in Synthesis Examples 1-4, the polycarbonate resins obtained in Synthesis Examples 5 and 6, an antioxidant, and a mold release agent were dry-mixed using a tumbler in the proportions (in parts by mass) indicated in Table 2 below. Each of the resultants was melt-kneaded using a twin-screw extruder (IPT type 35 mm co-rotating twin-screw extruder manufactured by IPEC Co. Ltd.) at a cylinder temperature of 260° C. and a vent pressure of 25 Torr, extruded as a strand, and pelletized to obtain pellets of transparent resin compositions. The evaluation results of the obtained resin compositions are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Com- Com- Com- Com- parative parative parative parative Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- ex- ex- ex- ex- ample ample ample ample ample ample ample ample ample ample ample ample 1 2 3 4 5 6 7 8 1 2 3 4 Comp- Polyester Synthesis 92 84 0 0 0 0 0 0 100 0 0 0 osition resin example 1 [parts by Synthesis 0 0 95 77 0 0 0 0 0 100 0 0 mass] Example 2 Synthesis 0 0 0 0 60 50 40 0 0 0 100 0 Example 3 Synthesis 0 0 0 0 0 0 0 70 0 0 0 100 Example 4 Poly- Synthesis 8 16 5 23 40 50 60 5 0 0 0 0 carbonate Example 5 resin Synthesis 0 0 0 0 0 0 0 25 0 0 0 0 [parts by Example 6 mass] Antioxidant AO-60 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [parts by PEP-36 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 mass] Mold NAA-180 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0 0.2 0.2 0.2 0 release M-2222SL 0 0 0 0 0 0 0 0.2 0 0 0 0.2 agent [parts by mass] Eval- Weight average 29000 29000 33000 30000 31000 29000 27000 31000 30000 33000 37000 34000 uation molecular results weight (Mw) Glass transition 150 150 146 145 143 143 143 141 151 146 142 146 temperature (Tg) [° C.] Refractive index (nd) 1.54 1.55 1.55 1.57 1.59 1.59 1.60 1.55 1.54 1.55 1.55 1.55 Abbe number (vd) 49.6 45.0 45.2 38.0 32.2 30.2 28.7 44.6 56.0 47.7 44.5 45.0 Continuous B B B B B B B A B′ B′ B′ B′ formability

[0182] The abbreviations in the table are defined as follows. [0183] AO-60: ADK STAB AO-60 manufactured by ADEKA Corporation [0184] PEP-36: ADK STAB PEP-36 manufactured by ADEKA Corporation [0185] NAA-180: NAA-180 manufactured by NOF Corporation [0186] M-2222SL: UNISTER M-2222SL manufactured by NOF Corporation

[0187] Compared to Comparative example 1 which used the same polyester resin, Examples 1 and 2 were able to realize lower Abbe numbers while maintaining almost the same refractive index, and achieved higher Tg (improved heat resistance). Compared to Comparative example 3, Examples 5 to 7 tend to have slightly higher refractive indices, but the resin compositions with reduced Abbe numbers could be obtained. Example 8 had a slightly reduced Abbe number and improved continuous moldability compared to Comparison Example 4.