Resin composition

Abstract

Provided is a thermoplastic resin composition having excellent optical characteristics, which does not impair the characteristics of an optical resin composition, has high flowability and good moldability, and has a composition capable of preventing gelation (increase in molecular weight). The polycarbonate resin contains a structural unit (A) derived from a diol represented by formula (1), and a structural unit (B) represented by formula (2) and / or a structural unit (C) represented by formula (3). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition containing a thermoplastic resin and a specific compounding agent. Background Art

[0002] As materials for optical lenses used in optical systems of various cameras such as cameras, integrated film cameras, and video cameras, optical glass or optical resins are used. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems of high material cost, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.

[0004] When using an optical resin as an optical lens, in addition to optical properties such as refractive index and Abbe number, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, heat and humidity resistance, etc. are also required. Especially in recent years, optical lenses with high refractive index and high heat resistance have been required, and various resins have been developed (Patent Documents 1 to 5).

[0005] Among them, a polycarbonate resin containing a structural unit (A) derived from a diol represented by the formula (1) has a high refractive index and is effective as an optical material; and its Tg is also high, and it is expected to be used as a high heat resistance optical material. On the other hand, due to the high Tg, it is necessary to increase the molding temperature during molding (Patent Document 6).

[0006] However, it is known that when compounding (extruding) various additives or during molding, a phenomenon of increased molecular weight easily occurs, resulting in uncontrollable failures. It is speculated that this may be due to the gelation reaction caused by the branching reaction.

[0007] Therefore, as a polycarbonate resin containing a structural unit (A) derived from a diol represented by the formula (1), a polycarbonate resin having a composition that can maintain a high refractive index and prevent the above-mentioned gelation (increase in molecular weight) within a range where there are no problems in practical use as an optical material is still sought.

[0008]

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018 - 2893

[0012] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2018-2894

[0013] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2018-2895

[0014] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2018-59074

[0015] Patent Document 5: WO2017 / 078073

[0016] Patent Document 6: Japanese Unexamined Patent Application Publication No. 2020-114907 Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] The present invention provides a thermoplastic resin composition having excellent optical properties, high fluidity, good moldability, and not impairing the properties of an optical resin composition. More specifically, as a polycarbonate resin containing a structural unit (A) derived from a diol represented by the following formula (1), a polycarbonate resin having a composition that can maintain a high refractive index and prevent the above gelation (increase in molecular weight) within a range not causing problems in practical use as an optical material is provided. The present invention also provides a polycarbonate resin having high reflow heat resistance.

[0019] Technical Means for Solving the Problems

[0020] The inventors of the present invention conducted intensive studies repeatedly to solve the problems of the prior art, and as a result, found that: by adding a specific compounding agent to a thermoplastic resin, a composition that can prevent gelation (increase in molecular weight) can be obtained, and a thermoplastic resin composition having a low Tg, high fluidity, good moldability, and excellent optical properties can be obtained, thereby completing the present invention.

[0021] That is, the present invention includes the following embodiments.

[0022] <1> A polycarbonate resin comprising: a structural unit (A) derived from a diol represented by the following formula (1); and a structural unit (B) represented by the following formula (2) and / or a structural unit (C) represented by the following formula (3).

[0023]

[0024] <2> A polycarbonate resin containing at least: a structural unit (A) derived from a diol represented by the following formula (1); and a structural unit (B) derived from a diol represented by the following formula (2),

[0025] The relationship between the total light transmittance before and after the reflow heat resistance test satisfies the following formula (I):

[0026] Total light transmittance (%) before reflow heat resistance test / Total light transmittance (%) after reflow heat resistance test = 0.9 to 1.3 (I).

[0027] <3>The polycarbonate resin according to <1> or <2> above, wherein the molar ratio (A:B + C) of the above structural unit (A) to the above structural unit (B) and / or the above structural unit (C) is 20:80 to 80:20.

[0028] <4>A polycarbonate resin composition comprising: the polycarbonate resin according to <1> or <2> above, and one or more of the compounds represented by the following formulas (4), (5), (6), (7) and (8).

[0029]

[0030] <5>The polycarbonate resin composition according to <3> above, wherein in the above polycarbonate resin composition, the content of the compounds represented by the above formulas (4), (5), (6), (7) and (8) is 1 ppm to 1% by mass.

[0031] <6>The polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above, wherein the glass transition temperature (Tg) is 230 to 290 °C.

[0032] <7>The polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above, wherein the refractive index is 1.570 to 1.645.

[0033] <8>The polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above, wherein the weight-average molecular weight (Mw) is 10,000 to 100,000.

[0034] <9>The polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above, wherein the weight-average molecular weight retention rate is 50% to 150%.

[0035] <10>An optical component containing the polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above.

[0036] <11>An optical lens containing the polycarbonate resin according to <1> or <2> above or the polycarbonate resin composition according to <4> above.

[0037] <12>An optical film containing the polycarbonate resin described in <1> or <2> above or the polycarbonate resin composition described in <4> above.

[0038] <13>A vehicle-mounted component containing the polycarbonate resin described in <1> or <2> above or the polycarbonate resin composition described in <4> above.

[0039] Effects of the Invention

[0040] According to the present invention, a thermoplastic resin composition having excellent optical properties can be provided, which has high fluidity, good moldability, can prevent gelation (increase in molecular weight), and does not impair the properties of the optical resin composition. Description of the Drawings

[0041] Figure 1 It is a reflow temperature distribution diagram obtained by performing a reflow heat resistance test on the resin composition of the present invention. Detailed Description

[0042] In the present invention, the thermoplastic resin can be any one of polycarbonate resin, polyester carbonate resin, and polyester resin. Hereinafter, the polycarbonate resin will be described as an example.

[0043] 1. Polycarbonate resin

[0044] The polycarbonate resin of the present invention contains a structural unit (A) derived from a diol represented by the following formula (1), and also contains a structural unit (B) represented by the following formula (2) and / or a structural unit (C) represented by the following formula (3).

[0045]

[0046] In one embodiment of the present invention, the polycarbonate resin contains a structural unit (A) derived from the diol represented by the above formula (1) and a structural unit (B) represented by the above formula (2).

[0047] In one embodiment of the present invention, the polycarbonate resin contains a structural unit (A) derived from the diol represented by the above formula (1) and a structural unit (C) represented by the above formula (3).

[0048] In one embodiment of the present invention, the polycarbonate resin contains a structural unit (A) derived from the diol represented by the above formula (1), a structural unit (B) represented by the above formula (2), and a structural unit (C) represented by the above formula (3).

[0049] As described above, in the case of a polycarbonate resin containing only the structural unit (A), the Tg becomes too high, the moldability is poor, and gelation due to branching may occur due to heating, there is a tendency for the molecular weight to increase, and it is likely to cause uncontrollable failures during extrusion or molding. However, by adding the structural unit (B) and / or the structural unit (C) to the structural unit (A), this unexpected increase in molecular weight can be controlled.

[0050] In one embodiment of the present invention, the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) may be 20∶80 to 80∶20, preferably 30∶70 to 70∶30, more preferably 40∶60 to 60∶40. In one embodiment of the present invention, the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) is 20∶80 to 80∶20. In a more preferred embodiment of the present invention, the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) is 30∶70 to 70∶30. In a further preferred embodiment of the present invention, the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) is 40∶60 to 60∶40. In one embodiment of the present invention, the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) can be, for example, 20∶80, 30∶70, 40∶60, 50∶50, 40∶60, 70∶30, 80∶20, etc. By the molar ratio (A∶B + C) of the above-mentioned structural unit (A) to the above-mentioned structural unit (B) and / or the above-mentioned structural unit (C) being in the above range, as described above, the increase in molecular weight can be controlled.

[0051] 2. Polycarbonate resin composition

[0052] The resin composition of the present invention contains the above polycarbonate resin and one or more of the compounds represented by the following formulas (4), (5), (6), (7), and (8). By the polycarbonate resin composition containing the above polycarbonate resin and one or more of the compounds represented by the following formulas (4), (5), (6), (7), and (8) as a compounding agent, a thermoplastic resin composition with high fluidity, good moldability, and excellent optical properties can be obtained, and this composition has a composition that can prevent gelation (increase in molecular weight) and does not impair the properties of the optical resin composition. By adding one or more of the compounds represented by the following formulas (4), (5), (6), (7), and (8) as a compounding agent to the above polycarbonate resin, the increase in molecular weight can be further suppressed.

[0053]

[0054]

[0055] In one embodiment of the present invention, a polycarbonate resin composition containing the above polycarbonate resin and a compound represented by the following formula (4) is provided. By containing the above polycarbonate resin and the compound represented by the following formula (4) as a compounding agent, a thermoplastic resin composition having high fluidity, good moldability, and excellent optical properties can be obtained, and the composition has a composition capable of preventing gelation (increase in molecular weight) and not impairing the properties of the optical resin composition.

[0056]

[0057] By adding the compound represented by the above formula (4) as a compounding agent to the above polycarbonate resin, an increase in molecular weight can be further suppressed.

[0058] In one embodiment of the present invention, in the polycarbonate resin composition, the content of the compounds represented by the above formulas (4), (5), (6), (7), and (8) may be 1 ppm to 1% by mass, preferably 100 ppm to 1% by mass, more preferably 500 to 1500 ppm, and further preferably 500 to 1000 ppm. In one embodiment of the present invention, a polycarbonate resin composition containing the compound represented by the above formula (4) in an amount of 1 ppm to 1% by mass in the above polycarbonate resin composition can be provided. In a preferred embodiment of the present invention, a polycarbonate resin composition containing the compound represented by the above formula (4) in an amount of 100 ppm to 1% by mass in the above polycarbonate resin composition can be provided. In a more preferred embodiment of the present invention, a polycarbonate resin composition containing the compound represented by the above formula (4) in an amount of 500 to 1500 ppm in the above polycarbonate resin composition can be provided. In a further preferred embodiment of the present invention, a polycarbonate resin composition containing the compound represented by the above formula (4) in an amount of 500 to 1000 ppm in the above polycarbonate resin composition can be provided. Since the above polycarbonate resin composition contains the compound represented by the above formula (4) in an amount within the above range, an increase in molecular weight can be further suppressed.

[0059] 3. Physical properties of polycarbonate resin composition

[0060] (1) Glass transition temperature (Tg)

[0061] Measurement is carried out using a differential scanning calorimeter (DSC).

[0062] Measuring equipment: Differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation

[0063] Heating rate: 10 °C / min

[0064] Gas flow environment: Nitrogen 20 ml / min

[0065] Sample pretreatment: Heating and melting at 300 °C

[0066] The glass transition temperature (Tg) of the polycarbonate resin composition of the present invention can be 230 - 290 °C, preferably 240 - 280 °C, more preferably 245 - 280 °C, and further preferably 250 - 270 °C. In one embodiment of the present invention, the glass transition temperature (Tg) of the polycarbonate resin composition is 230 - 290 °C. In a preferred embodiment of the present invention, the glass transition temperature (Tg) of the polycarbonate resin composition is 240 - 280 °C. In a more preferred embodiment of the present invention, the glass transition temperature (Tg) of the polycarbonate resin composition is 245 - 280 °C. In a further preferred embodiment of the present invention, the glass transition temperature (Tg) of the polycarbonate resin composition is 250 - 270 °C.

[0067] (2) Refractive index (nd)

[0068] Dissolve the polycarbonate resin or polycarbonate resin composition with dichloromethane to prepare a 10% by mass resin solution. Measure 9.2 g of the prepared solution into a 150 ml disposable measuring cup manufactured by Daisuke Teraoka Co., Ltd., dry it at room temperature for 24 hours, and then dry it at 120 °C for 24 hours to produce a test piece with a thickness of 0.5 mm, and measure it using the following device and wavelength.

[0069] Measuring device: Abbemat Mw manufactured by Anton Paar

[0070] Measuring wavelength: 587.6 nm

[0071] The refractive index of the polycarbonate resin composition of the present invention can be 1.570 - 1.645, preferably 1.580 - 1.640, more preferably 1.590 - 1.630, and further preferably 1.600 - 1.620. In one embodiment of the present invention, the refractive index of the polycarbonate resin composition is 1.570 - 1.645. In a preferred embodiment of the present invention, the refractive index of the polycarbonate resin composition is 1.580 - 1.640. In a more preferred embodiment of the present invention, the refractive index of the polycarbonate resin composition is 1.590 - 1.630. In a further preferred embodiment of the present invention, the refractive index of the polycarbonate resin composition is 1.600 - 1.620.

[0072] (3) Weight-average molecular weight (Mw)

[0073] The polystyrene-reduced molecular weight (Mw) of the polycarbonate resin or polycarbonate resin composition is measured by gel permeation chromatography (GPC) under the following conditions.

[0074] Measurement conditions

[0075] Measurement equipment: HLC-8320GPC manufactured by Tosoh Corporation

[0076] Columns: Shodex K-G + K-805L × 2 pieces + K-800D

[0077] Eluent: chloroform

[0078] Temperature: column thermostat at 40 °C

[0079] Flow rate: 1.0 ml / min

[0080] Concentration: 0.1 wt / vol%

[0081] Injection volume: 100 μl

[0082] Pretreatment: filtration through a 0.45 μm filter

[0083] Detection equipment: UV refractometer

[0084] Standard polystyrene: EasiCal Type PS-1 polystyrene manufactured by GL Sciences Inc.

[0085] The weight-average molecular weight (Mw) of the polycarbonate resin composition of the present invention can be 10,000 to 100,000, preferably 20,000 to 70,000, more preferably 30,000 to 60,000, and further preferably 30,000 to 55,000. In one embodiment of the present invention, the weight-average molecular weight (Mw) of the polycarbonate resin composition is 10,000 to 100,000. In a preferred embodiment of the present invention, the weight-average molecular weight (Mw) of the polycarbonate resin composition is 20,000 to 70,000. In a more preferred embodiment of the present invention, the weight-average molecular weight (Mw) of the polycarbonate resin composition is 30,000 to 60,000. In a further preferred embodiment of the present invention, the weight-average molecular weight (Mw) of the polycarbonate resin composition is 30,000 to 55,000.

[0086] (4) Molecular weight (Mw) after heating

[0087] 5 g of the obtained polycarbonate resin or polycarbonate resin composition is added to a test tube. The test tube is heated at 380 °C for 30 minutes using a block heater, and Mw is measured in the same manner as in (3) above.

[0088] The molecular weight (Mw) of the polycarbonate resin composition of the present invention can be 5,000 to 150,000, preferably 10,000 to 100,000, more preferably 20,000 to 70,000, and still more preferably 20,000 to 50,000. In one embodiment of the present invention, the molecular weight (Mw) of the polycarbonate resin composition after heating is 5,000 to 150,000. In a more preferred embodiment of the present invention, the molecular weight (Mw) of the polycarbonate resin composition after heating is 10,000 to 100,000. In a still more preferred embodiment of the present invention, the molecular weight (Mw) of the polycarbonate resin composition after heating is 20,000 to 50,000.

[0089] (5) Mw retention rate (%)

[0090] The molecular weight (Mw) measured in (3) and (4) above is calculated by the following (Formula 1).

[0091] Mw retention rate (%) = molecular weight (Mw) after heating / molecular weight (Mw) × 100 (Formula 1)

[0092] The Mw retention rate of the polycarbonate resin composition of the present invention can be 50% to 150%, preferably 60% to 150%, more preferably 60% to 100%, still more preferably 70% to 100%, and even more preferably 80% to 90%. In one embodiment of the present invention, the Mw retention rate of the polycarbonate resin composition is 50% to 150%. In a preferred embodiment of the present invention, the Mw retention rate of the polycarbonate resin composition is 60% to 150%. In a more preferred embodiment of the present invention, the Mw retention rate of the polycarbonate resin composition is 60% to 100%. In a still more preferred embodiment of the present invention, the Mw retention rate of the polycarbonate resin composition is 70% to 100%. In an even more preferred embodiment of the present invention, the Mw retention rate of the polycarbonate resin composition is 80% to 90%.

[0093] (6) Reflow soldering heat resistance

[0094] In optical components, for example, in a part of an in-vehicle camera or a precision lens for sensing, labor saving is required in the manufacturing process of a resin lens, so an optical resin having reflow heat resistance is needed. Generally, the reflow soldering process for soldering electronic components needs to be heated to a maximum temperature of about 260°C. Existing thermoplastic resin lenses do not have the heat resistance to withstand this process, and a separate process for assembling the lens is required. However, when the resin of the present invention is used, since it has heat resistance that can also withstand a soldering reflow process such as 260°C, it is not necessary to separately assemble the lens after the reflow soldering process, and labor saving in the manufacturing process is expected.

[0095] The polycarbonate resin composition of the present invention has good reflow heat resistance. The reflow heat resistance of the polycarbonate resin composition of the present invention is judged based on IPC / JEDEC J-STD-020E for a test piece with a thickness of 0.8 mm and a test piece with a thickness of 2.0 mm.

[0096] · Molding of the 0.8 mm thick test piece

[0097] The obtained polycarbonate resin is molded into a circular plate with a thickness of 0.8 mm and a diameter of 4 cm using a compression molding machine.

[0098] Molding machine: Compression molding machine NS-37 manufactured by Shindo Metal Industry Co., Ltd.

[0099] Molding conditions: Compression pressure 210 kgf / cm 2 , Compression temperature 300 °C × 5 min

[0100] · Molding of the 2.0 mm thick test piece

[0101] The obtained polycarbonate resin is molded into a circular plate with a thickness of 2.0 mm and a diameter of 4 cm using a compression molding machine.

[0102] Molding machine: Compression molding machine NS-37 manufactured by Shindo Metal Industry Co., Ltd.

[0103] Molding conditions: Compression pressure 210 kgf / cm 2 , Compression temperature 300 °C × 5 min

[0104] · Reflow heat resistance test

[0105] The reflow temperature distribution is measured under the following conditions. The obtained reflow temperature distribution is shown in Figure 1 .

[0106] Apparatus: TNV-568EM-P reflow oven manufactured by Tamura Seisakusho Co., Ltd.

[0107] Number of repetitions: 3 times

[0108] · Judgment

[0109] Judgment is made based on the change in the total light transmittance (%) before and after the reflow heat resistance test and the change in the yellow index (YI) of the molded sheet. That is, it is calculated by the following formula.

[0110] Change in total light transmittance = Total light transmittance (%) before reflow test / Total light transmittance (%) after reflow test

[0111] Change in YI of molded sheet = YI before reflow test / YI after reflow test

[0112] The closer the change in total light transmittance and the change in YI are to 1.0, the less the change caused by reflow soldering and the higher the reflow soldering heat resistance.

[0113] (7) Total light transmittance (%)

[0114] The measurement of the total light transmittance (%) of the formed sheet is as follows.

[0115] · Total light transmittance (%)

[0116] The measurement is carried out in accordance with the JIS-K-7361 standard using the following device.

[0117] Measuring device: Nippon Denshoku haze meter SH-7000

[0118] Measuring wavelength: 380 nm to 780 nm

[0119] (8) Yellow index (YI) of molded sheet

[0120] The measurement of the YI of the formed sheet is as follows.

[0121] · YI of the formed sheet

[0122] The measurement is carried out in accordance with the JIS-K-7373 standard using the following device.

[0123] Measuring device: Nippon Denshoku haze meter SH-7000

[0124] Measuring wavelength: 380 nm to 780 nm

[0125] (9) Yellow index (YI) of solution

[0126] Dissolve 6 g of the polycarbonate resin composition in 60 ml of dichloromethane to prepare a resin solution with a concentration of 0.1 g / mL. Measure 60 ml of the prepared solution into a quartz cuvette and carry out the measurement using the following device and wavelength.

[0127] Measuring device: Nippon Denshoku haze meter SH-7000

[0128] Measuring wavelength: 380 nm to 780 nm

[0129] 4. Manufacturing method of polycarbonate resin

[0130] The polycarbonate resin can be manufactured by a conventional method.

[0131] In the phosgene method, a diol is reacted with phosgene in the presence of a conventional acid binder and a solvent. As the acid binder, for example, pyridine, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. In addition, as the solvent, for example, dichloromethane, chloroform, etc. can be used. Moreover, in order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride is preferably used. Further, a monofunctional compound such as phenol, p-tert-butylphenol, p-cumylphenol, or an alkyl-substituted phenol is preferably added as a molecular weight regulator in order to adjust the degree of polymerization. In addition, an antioxidant such as sodium sulfite or sodium dithionite, or a branching agent such as phloroglucinol or isatin bisphenol can be added in a small amount as needed. The reaction temperature is usually suitably set in the range of 0 to 150°C, preferably 5 to 40°C. The reaction time is affected by the reaction temperature and is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. In addition, during the reaction, it is preferable to maintain the pH value of the reaction system at 10 or more.

[0132] On the other hand, in the transesterification method, a diol is mixed with a diaryl carbonate and reacted under reduced pressure in a high-temperature environment. As examples of the diaryl carbonate, diaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate can be cited. These compounds can be used alone or in combination of two or more. The reaction is usually carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C. In addition, regarding the degree of reduced pressure, the phenols derived from the diaryl carbonate generated by the transesterification reaction are distilled out of the system so that the final vacuum degree preferably reaches 1 mmHg or less. The reaction time is affected by the reaction temperature, the degree of reduced pressure, etc., and is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas environment such as nitrogen or argon.

[0133] The content of the dicarboxylic acid chloride or phosgene, or the diaryl carbonate component is preferably less than 42 mol%, more preferably less than 30 mol%, and further preferably less than 20 mol% relative to 100 mol% of the dicarboxylic acid component.

[0134] <Additive>

[0135] Additives such as a heat stabilizer, an antioxidant, a mold release agent, a plasticizer, a filler, an ultraviolet absorber, a rust inhibitor, a dispersant, an antifoaming agent, and a leveling agent can be appropriately added to the thermoplastic resin of the present invention as needed to prepare a thermoplastic resin composition for use.

[0136] As a mold release agent, preferably, 90% by weight or more thereof is composed of an ester of an alcohol and a fatty acid. As the ester of an alcohol and a fatty acid, specifically, an ester of a monohydric alcohol and a fatty acid and / or a partial ester or a full ester of a polyhydric alcohol and a fatty acid can be cited. As the above-mentioned ester of a monohydric alcohol and a fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred. In addition, as the partial ester or full ester of a polyhydric alcohol and a fatty acid, a partial ester or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred. As the ester of a monohydric alcohol and a saturated fatty acid, specifically, stearyl stearate, palmitic acid palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be cited, and stearyl stearate is preferred.

[0137] As the partial ester or full ester of a polyhydric alcohol and a saturated fatty acid, specifically, glycerol monostearate, glycerol distearate, glycerol tristearate, sorbitan monostearate, glycerol monobehenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetranonanoate, propylene glycol monostearate, biphenol acid ester, sorbitan monostearate anhydride, 2-ethylhexyl stearate, full esters or partial esters of dipentaerythritol such as dipentaerythritol hexastearate, etc. can be cited. Among these esters, it is preferable to use glycerol monostearate, glycerol tristearate, pentaerythritol tetrastearate, and a mixture of glycerol tristearate and stearyl stearate.

[0138] When the mold release agent is set to 100% by weight, the amount of the above-mentioned ester in the mold release agent is preferably 90% by weight or more, more preferably 95% by weight or more.

[0139] As the mold release agent compounded in the thermoplastic resin composition, relative to 100 parts by weight of the thermoplastic resin, it 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, and still more preferably in the range of 0.02 to 0.5 parts by weight.

[0140] As the heat stabilizer, a phosphorus-based heat stabilizer, a sulfur-based heat stabilizer, and a hindered phenol-based heat stabilizer can be cited.

[0141] Among the phosphorus-based heat stabilizers, it is preferable to use tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite.

[0142] As the content of the phosphorus-based heat stabilizer of the thermoplastic resin, relative to 100 parts by weight of the thermoplastic resin, it is preferably 0.001 to 0.2 parts by weight.

[0143] Among the hindered phenol-based heat stabilizers, it is particularly preferable to use octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0144] As the content of the hindered phenol-based heat stabilizer in the thermoplastic resin, it is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0145] As the ultraviolet absorber, at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers is preferred.

[0146] Among the benzotriazole-based ultraviolet absorbers, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are more preferred. As the benzophenone-based ultraviolet absorber, 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone can be cited. As the triazine-based ultraviolet absorber, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5[(octyl)oxy]-phenol, etc. can be cited. As the cyclic iminoester-based ultraviolet absorber, 2,2'-p-phenylene bis(3,1-benzoxazine-4-one) is particularly preferred.

[0147] Relative to 100 parts by weight of the thermoplastic resin, the compounding amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight. When the compounding amount is within this range, the thermoplastic resin molded article can be given sufficient weather resistance according to the use.

[0148] <Manufacturing method of the resin composition>

[0149] The manufacturing method of the resin composition is not particularly limited and can be manufactured by known methods. In one embodiment, the manufacturing method of the resin composition includes a step of mixing the thermoplastic resin and the compounding agent. It may further include a step of mixing at least one of a solvent and an additive. For example, by sequentially or simultaneously adding the compounding agent and the additive to the thermoplastic resin and mixing, the resin composition can be manufactured. The mixing step can be carried out by a conventional method. For example, there are a method of kneading using an extruder, a method of dissolving the resin and the compounding agent in a solvent (such as dichloromethane or THF, etc.) to form a solution and then mixing the solutions with each other, etc.

[0150] 2. Molded product

[0151] The resin composition of the present invention is suitable for optical components. In one embodiment of the present invention, an optical component containing the resin composition of the present invention is provided. In one embodiment of the present invention, the optical component includes, but is not limited to, an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a base, a filter, a hard coating film, etc. The resin composition of the present invention has high fluidity and can be formed by the casting method, so it is particularly suitable for manufacturing thin optical components. In a preferred embodiment of the present invention, the optical component manufactured using the resin composition of the present invention can be an optical lens. In another preferred embodiment of the present invention, the optical component manufactured using the resin composition of the present invention can be an optical film.

[0152] When manufacturing an optical component containing the resin composition of the present invention by injection molding, in one embodiment, it is preferably molded under the conditions of a barrel temperature of 260 to 350 °C and a mold temperature of 90 to 170 °C. More preferably, it is molded under the conditions of a barrel temperature of 270 to 320 °C and a mold temperature of 100 to 160 °C. When the barrel temperature is higher than 350 °C, the resin composition is liable to decompose and color; when it is lower than 260 °C, the melt viscosity increases, liable to cause molding difficulties. In addition, when the mold temperature is higher than 170 °C, it is liable to make it difficult to take out the molded sheet formed by the resin composition from the mold; when the mold temperature is lower than 90 °C, the resin cures prematurely in the mold during molding, liable to make the shape of the molded sheet difficult to control or difficult to fully transfer the shape given by the mold.

[0153] When manufacturing an optical component containing the resin composition of the present invention by injection molding, in another embodiment, it is preferably molded under the conditions of a barrel temperature of 350 to 450 °C and a mold temperature of 180 to 290 °C. In this embodiment, more preferably, it is molded under the conditions of a barrel temperature of 360 to 420 °C and a mold temperature of 190 to 280 °C. When the barrel temperature is higher than 450 °C, the resin composition is liable to decompose and color; when it is lower than 350 °C, the melt viscosity increases, liable to cause molding difficulties. In addition, when the mold temperature is higher than 280 °C, it is liable to make it difficult to take out the molded sheet formed by the resin composition from the mold; when the mold temperature is lower than 180 °C, the resin cures prematurely in the mold during molding, liable to make the shape of the molded sheet difficult to control or difficult to fully transfer the shape given by the mold.

[0154] <Optical Lens>

[0155] In one embodiment of the present invention, the resin composition is applicable to optical lenses. The optical lenses manufactured using the resin composition of the present invention have a high refractive index and excellent heat resistance, and thus can be used in fields such as telescopes, binoculars, and television projectors, which have previously used expensive high-refractive-index glass lenses, and are therefore extremely useful.

[0156] The optical lenses of the present invention are preferably implemented in the form of aspherical lenses as needed. Since an aspherical lens can achieve substantially zero spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, and weight reduction and a reduction in molding costs can be achieved. Therefore, aspherical lenses are very useful in optical lenses, particularly as camera lenses.

[0157] In addition, the optical lenses of the present invention have high molding fluidity, and are therefore particularly useful as materials for thin and small complex-shaped optical lenses. As specific lens dimensions, the thickness of the central portion is preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further preferably 0.1 to 2.0 mm. In addition, the diameter is preferably 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and further preferably 3.0 to 10.0 mm. In addition, as its shape, a meniscus lens with one convex surface and one concave surface is preferred.

[0158] The optical lenses of the present invention can be molded by any method such as mold molding, cutting, grinding, laser processing, electrical discharge machining, and etching. Among them, mold molding is more preferred from the perspective of manufacturing cost.

[0159] <Optical film>

[0160] In one embodiment of the present invention, the resin composition is applicable to optical films. The optical films manufactured using the polycarbonate resin of the present invention have excellent transparency and heat resistance, and are therefore suitable for use in films for liquid crystal substrates, optical memory cards, etc.

[0161] In order to avoid foreign matter from mixing into the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably Class 6 or lower, and more preferably Class 5 or lower.

[0162] <Automotive components>

[0163] In one embodiment of the present invention, the resin composition is applicable to automotive components. The automotive components manufactured using the polycarbonate resin composition of the present invention have excellent molding fluidity, transparency, heat resistance, and reflow soldering heat resistance, and are therefore suitable for use in automotive cameras or precision lenses for sensing, etc.

[0164] Examples

[0165] Hereinafter, examples and comparative examples of the present invention are given to describe the invention in detail, but the present invention is not limited to these examples.

[0166] (Example 1)

[0167] (Step 1)

[0168] 49.1 g of spiro[fluorene-9,9'-xanthene]-3',6'-diol (SFX, manufactured by Taoka Chemical Industry Co., Ltd.) and 50.9 g of bisphenol fluorene (BCFL, manufactured by Honshu Chemical Industry Co., Ltd.) were added to 500 ml of a 9 w / w% aqueous sodium hydroxide solution, that is, added in accordance with SFX:BCFL = 50:50 (mol%), and then 0.5 g of sodium dithionite was added and dissolved. 300 ml of dichloromethane and 0.1 g of triethylbenzylammonium chloride (TEBAC, manufactured by Fujifilm Wako Pure Chemical Corporation) were added to this solution. While stirring, the solution temperature was set to 20°C, and then 37.3 g of phosgene was blown in over 30 minutes.

[0169] (Step 2)

[0170] After the blowing-in of phosgene was completed, 2.53 g of p-tert-butylphenol (PTBP) dissolved in 50 ml of dichloromethane was added, and the mixture was vigorously stirred for 7 minutes to emulsify it, and then 0.5 ml of triethylamine was added as a polymerization catalyst, and polymerization was carried out for about 30 minutes.

[0171] (Subsequent steps)

[0172] The polymerization solution was separated into an aqueous layer and an organic layer, the organic layer was neutralized with phosphoric acid, and washed repeatedly with pure water until the pH value of the washing solution reached pH = 7.0. The organic solvent was evaporated from the refined polycarbonate resin to obtain polycarbonate resin powder. The polycarbonate resin powder was dried at 120°C for 24 hours to completely evaporate the solvent.

[0173] The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0174] (Example 2)

[0175] (Additive mixing step)

[0176] 5 g of the polycarbonate resin obtained in Example 1, 0.005 g of the compound shown in formula (4) (AO-60 manufactured by ADEKA Corporation), and 50 ml of dichloromethane were mixed and dissolved. The obtained solution was dried at 120°C for 24 hours to remove dichloromethane, and a polycarbonate resin composition was obtained. The physical properties of the obtained polycarbonate resin composition are shown in Table 1.

[0177] (Examples 3, 5, 7, 12, 14 and Comparative Example 1)

[0178] BCFL was replaced with 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (TMC, manufactured by Honshu Chemical Industry Co., Ltd.) in the ratio shown in the table, and the same operations as in Example 1 were carried out to obtain a polycarbonate resin. The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0179] (Examples 4, 6, 8 to 11, 13, 15 and Comparative Example 2)

[0180] Except that the mixing amount of AO-60 was replaced with the amount shown in the table, the same operations as in Example 2 were carried out to obtain a polycarbonate resin. The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0181] (Comparative Examples 3 to 7)

[0182] Except that SFX and BCFL were replaced with TMC and BCFL in the ratio shown in the table, the same operations as in Example 1 were carried out to obtain a polycarbonate resin. The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0183] [Table 1]

[0184]

[0185] ※ The test piece for refractive index measurement became cloudy, so the measurement of refractive index could not be achieved.

[0186] (Example 16)

[0187] (Step 1)

[0188] As raw materials, 63.8 g (0.18 mol) of spiro[fluorene-9,9'-xanthene]-3',6'-diol (SFX, manufactured by Taoka Chemical Industry Co., Ltd.) and 36.2 g (0.12 mol) of 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (TMC, manufactured by Honshu Chemical Industry Co., Ltd.) were added, that is, added according to SFX∶TMC = 60∶40 (mol%), and 0.5 g of sodium dithionite was also added and dissolved. 300 ml of dichloromethane and 0.1 g of triethylbenzylammonium chloride (TEBAC, manufactured by Fujifilm Wako Pure Chemical Corporation) were added to this solution. While stirring, the solution temperature was set to 20°C, and 40.5 g of phosgene was blown in over 30 minutes.

[0189] (Step 2)

[0190] After the blowing-in of phosgene was completed, 2.74 g of p-tert-butylphenol (PTBP) dissolved in 50 ml of dichloromethane was added, and it was vigorously stirred for 7 minutes to emulsify it, and then 0.5 ml of triethylamine was added as a polymerization catalyst, and polymerization was carried out for about 30 minutes.

[0191] (Subsequent steps)

[0192] The polymerization solution was separated into an aqueous layer and an organic layer. The organic layer was neutralized with phosphoric acid and washed repeatedly with pure water until the pH value of the washing solution reached pH = 7.0. The organic solvent was evaporated from the refined polycarbonate resin to obtain polycarbonate resin powder. The polycarbonate resin powder was dried at 120 °C for 24 hours to completely evaporate the solvent.

[0193] The reflow heat resistance of the polycarbonate resins obtained in Example 16 and Comparative Example 4 is shown together in Table 2.

[0194] [Table 2]

[0195]

[0196] In addition, the Tg of the obtained polycarbonate resin was 260 °C, nd was 1.613, and Mw was 41,600. The physical properties of the obtained polycarbonate resin are shown in Table 3.

[0197] (Example 16-1)

[0198] 2 kg of the polycarbonate resin obtained in Example 7, 2 g of AO-60 (1000 ppm) as an additive, 0.6 g (300 ppm) of ADEKASTAB PEP-36 (manufactured by ADEKA Corporation), and 3.0 g (1500 ppm) of UNISTER H-476 (manufactured by NOF Corporation) were mixed and melt-kneaded using a twin-screw kneading extruder TEM-18 (manufactured by Shibaura Machine Co., Ltd.) at a barrel temperature of 350 °C and a discharge rate of 4 kg / hr to obtain pellets of a polycarbonate resin composition. The physical properties of the obtained polycarbonate resin composition are shown in Table 3.

[0199] (Examples 16-2 to 16-3)

[0200] Except for replacing with the additives described in Table 3, the same operation as in Example 16-1 was performed to obtain pellets of a polycarbonate resin composition. The physical properties of the obtained polycarbonate resin composition are shown in Table 3.

[0201] (Example 16-a)

[0202] Except for not adding additives, the same operation as in Example 16-1 was performed to obtain pellets of a polycarbonate resin. The physical properties of the obtained polycarbonate resin are shown in Table 3.

[0203] [Table 3]

[0204]

[0205] As shown in Tables 1 to 3, the resin composition of the present invention has a composition with high fluidity, good moldability, capable of preventing gelation (increase in molecular weight) and not impairing the properties of the optical resin composition, and is a thermoplastic resin composition with high reflow heat resistance and excellent optical properties. According to the present invention, optical components such as optical lenses and optical films or automotive components can be precisely molded from this resin composition.

Claims

1. A polycarbonate resin, characterized in that, Comprising: A structural unit A derived from a diol represented by the following formula (1); and A structural unit B represented by the following formula (2) and / or a structural unit C represented by the following formula (3), 2. A polycarbonate resin, characterized in that, At least comprising: A structural unit A derived from a diol represented by the following formula (1); and A structural unit B derived from a diol represented by the following formula (2), The relationship between the total light transmittance before and after the reflow heat resistance test satisfies the relationship of the following formula (I): Total light transmittance before reflow heat resistance test (%) / Total light transmittance after reflow heat resistance test (%) = 0.9 to 1.3 (I).

3. The polycarbonate resin according to claim 1 or 2, wherein The molar ratio A:(B + C) of the structural unit A to the structural unit B and / or the structural unit C is 20:80 to 80:

20.

4. A polycarbonate resin composition, wherein It contains the polycarbonate resin according to claim 1 or 2, and one or more of the compounds represented by the following formulas (4), (5), (6), (7) and (8), 5. The polycarbonate resin composition according to claim 4, wherein In the polycarbonate resin composition, the compounds represented by the formulas (4), (5), (6), (7) and (8) are contained in an amount of 1 ppm to 1% by mass.

6. The polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4, wherein The glass transition temperature (Tg) is 230 to 290 °C.

7. The polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4, wherein The refractive index is 1.570 to 1.

645.

8. The polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4, wherein The weight-average molecular weight (Mw) is 10,000 to 100,000.

9. The polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4, wherein The weight-average molecular weight retention rate is 50% to 150%.

10. An optical component, characterized in that ， Contains the polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4.

11. An optical lens, characterized in that ， Contains the polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4.

12. An optical film, characterized in that ， Contains the polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4.

13. A vehicle-mounted component, characterized in that ， Contains the polycarbonate resin according to claim 1 or 2 or the polycarbonate resin composition according to claim 4.

Images